{"version":"1.0.0","segments":[{"speaker":null,"startTime":2.07,"endTime":4.68,"body":"Kevin: Welcome to Innovate and React."},{"speaker":null,"startTime":5.82,"endTime":10.17,"body":"In today's episode, we will betalking about the HSAB concept."},{"speaker":null,"startTime":10.92,"endTime":16.44,"body":"I'm sure every chemist has comeacross this concept at least"},{"speaker":null,"startTime":16.44,"endTime":22.23,"body":"once and maybe even used it topredict the outcome of reactions."},{"speaker":null,"startTime":22.93,"endTime":30.28,"body":"However, the HSAB concept mightnot be as complete as we think, and"},{"speaker":null,"startTime":30.58,"endTime":37.125,"body":"there are different methods to betterpredict the outcome of reactions by"},{"speaker":null,"startTime":37.125,"endTime":45.22,"body":"using nucleophilicity, and today I'mtalking to Justus Reitz, who is also"},{"speaker":null,"startTime":45.22,"endTime":48.34,"body":"studying at TU Dortmund University."},{"speaker":null,"startTime":49.34,"endTime":51.32,"body":"Maybe introduce herself a bit."},{"speaker":null,"startTime":51.32,"endTime":51.86,"body":"Justus: Hey Kevin."},{"speaker":null,"startTime":51.96,"endTime":52.77,"body":"Thanks for having me."},{"speaker":null,"startTime":53.46,"endTime":53.97,"body":"Yeah."},{"speaker":null,"startTime":54.09,"endTime":59.71,"body":"Uh, I have studied chemistry atthe TU Dortmund and did my PhD"},{"speaker":null,"startTime":59.71,"endTime":64.06,"body":"studies in the group of ProfessorHansmann in the organic chemistry."},{"speaker":null,"startTime":64.765,"endTime":71.365,"body":"And during my PhD studies, I dealt within stable or at least very highly reactive"},{"speaker":null,"startTime":71.395,"endTime":77.915,"body":"molecules and how to basically stabilizethem, how to, use them in reactions."},{"speaker":null,"startTime":77.915,"endTime":82.565,"body":"And also I had nice collaborationprojects with, uh, for example, a"},{"speaker":null,"startTime":82.565,"endTime":86.495,"body":"group in Munich, which researchersnucleophilicity and Molecules."},{"speaker":null,"startTime":86.5,"endTime":86.6,"body":"Mm-hmm."},{"speaker":null,"startTime":86.945,"endTime":91.965,"body":"And there we had collaboration projectsto really determine nucleophilicity"},{"speaker":null,"startTime":91.985,"endTime":93.665,"body":"and how you can control this."},{"speaker":null,"startTime":94.205,"endTime":94.535,"body":"Mm-hmm."},{"speaker":null,"startTime":95.285,"endTime":95.765,"body":"Kevin: And."},{"speaker":null,"startTime":96.65,"endTime":103.37,"body":"What is the, well, the main conceptto, uh, describe this from what"},{"speaker":null,"startTime":103.42,"endTime":108.58,"body":"I think all chemistry studentslearn this, uh, HSAB concept is"},{"speaker":null,"startTime":108.58,"endTime":113.39,"body":"one of the methods of describinghow nucleophiles and electrophiles"},{"speaker":null,"startTime":113.45,"endTime":115.31,"body":"interact, which with each other."},{"speaker":null,"startTime":115.76,"endTime":120.706,"body":"Justus: Yeah, they're the, so the groupin Munich, which I had the collaboration"},{"speaker":null,"startTime":120.706,"endTime":125.836,"body":"with is, uh, Mayr group, or also nowthe group, Mayr was the one who, uh,"},{"speaker":null,"startTime":125.866,"endTime":128.176,"body":"developed the scale of nucle fluidity."},{"speaker":null,"startTime":128.176,"endTime":132.911,"body":"So really giving nucleophiles, uh,value to measure their strength."},{"speaker":null,"startTime":133.171,"endTime":133.591,"body":"Mm-hmm."},{"speaker":null,"startTime":134.146,"endTime":138.086,"body":"And determine how fast they basicallycan react with electrophiles."},{"speaker":null,"startTime":138.106,"endTime":142.666,"body":"And if they can react with electrophilesat, at least at a sensible rate."},{"speaker":null,"startTime":143.071,"endTime":149.301,"body":"And, um, this was developed by Mayrand Ofial took this now over after Mayr"},{"speaker":null,"startTime":149.461,"endTime":159.151,"body":"retired and the HSAB concept, the Mayrgroup had a paper about in 2011 discussing"},{"speaker":null,"startTime":159.151,"endTime":165.001,"body":"that the HSAB treatment of these ambientnucleophiles, so nucleophiles with"},{"speaker":null,"startTime":165.361,"endTime":167.671,"body":"two reaction sites and determining"},{"speaker":null,"startTime":167.721,"endTime":171.801,"body":"which site would react withelectro files given on whether"},{"speaker":null,"startTime":171.801,"endTime":173.721,"body":"there is a hard site, so mm-hmm."},{"speaker":null,"startTime":174.141,"endTime":178.611,"body":"Small and high charge, or a soft site."},{"speaker":null,"startTime":178.911,"endTime":182.931,"body":"So bigger electron densitydistribution, basically."},{"speaker":null,"startTime":182.931,"endTime":182.932,"body":"Mm-hmm."},{"speaker":null,"startTime":183.006,"endTime":183.496,"body":"What are"},{"speaker":null,"startTime":183.496,"endTime":185.531,"body":"Kevin: examples, uh, for that?"},{"speaker":null,"startTime":185.531,"endTime":187.481,"body":"For a hard base, for example."},{"speaker":null,"startTime":187.881,"endTime":191.961,"body":"Justus: It's often explained with metalswhere you can imagine this very easily,"},{"speaker":null,"startTime":191.961,"endTime":194.931,"body":"like gold three plus gold one plus."},{"speaker":null,"startTime":194.936,"endTime":195.176,"body":"Mm-hmm."},{"speaker":null,"startTime":195.256,"endTime":200.661,"body":"With gold three plus being the softerLewis-acid basically, or being the"},{"speaker":null,"startTime":200.661,"endTime":204.021,"body":"soft, uh, electrophile in this case."},{"speaker":null,"startTime":204.111,"endTime":204.351,"body":"Mm-hmm."},{"speaker":null,"startTime":204.771,"endTime":209.451,"body":"Uh, so basically just highercharge and smaller iron radius."},{"speaker":null,"startTime":209.781,"endTime":210.981,"body":"And of course, in."},{"speaker":null,"startTime":211.731,"endTime":213.171,"body":"Organic, uh, chemistry."},{"speaker":null,"startTime":213.171,"endTime":214.311,"body":"You can also talk about this."},{"speaker":null,"startTime":214.311,"endTime":214.401,"body":"Mm-hmm."},{"speaker":null,"startTime":214.731,"endTime":220.761,"body":"For example, strong nucleophiles, uh,which are organic, that, uh, are used on"},{"speaker":null,"startTime":220.761,"endTime":224.746,"body":"a daily basis in labs are, for example,Triphenyl phosphine or something."},{"speaker":null,"startTime":224.866,"endTime":225.016,"body":"Mm-hmm."},{"speaker":null,"startTime":225.736,"endTime":231.511,"body":"And they are just, values can begiven with, relation to our standard."},{"speaker":null,"startTime":231.571,"endTime":237.451,"body":"And there for, there were alreadyattempts before Mayr did this, uh, to"},{"speaker":null,"startTime":237.451,"endTime":242.261,"body":"make a general nucleophilicity scaleand they were referenced, for example,"},{"speaker":null,"startTime":242.261,"endTime":247.241,"body":"to methyl bromide and as a standardelectrophile and so on with a value one."},{"speaker":null,"startTime":247.241,"endTime":251.711,"body":"And then you just give differentvalues depending on just how fast a"},{"speaker":null,"startTime":251.711,"endTime":253.516,"body":"nucleophile reacts with this and so on."},{"speaker":null,"startTime":253.516,"endTime":253.796,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":254.171,"endTime":260.706,"body":"So you have a standard and then youthrow different electro electrophiles"},{"speaker":null,"startTime":260.766,"endTime":267.426,"body":"on it, and then you compare that withdifferent nucleophiles and the speed."},{"speaker":null,"startTime":268.026,"endTime":270.066,"body":"Can then be, okay, thisis faster than this."},{"speaker":null,"startTime":270.066,"endTime":275.406,"body":"So it's in the scale higher, but there areno distinct values that you can measure."},{"speaker":null,"startTime":276.336,"endTime":281.136,"body":"Justus: Uh, you measure distinct values,but basically to have a comparability,"},{"speaker":null,"startTime":281.136,"endTime":284.916,"body":"to have useful number values."},{"speaker":null,"startTime":284.966,"endTime":289.256,"body":"I mean, if just for example,nucleophile a react with electrophile"},{"speaker":null,"startTime":289.256,"endTime":291.726,"body":"B and you give a reaction rate."},{"speaker":null,"startTime":291.936,"endTime":292.056,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":292.296,"endTime":294.276,"body":"Justus: This is not reallyuseful in everyday chemistry."},{"speaker":null,"startTime":294.426,"endTime":299.576,"body":"And to make this useful as a reallyvalue number, they made this in"},{"speaker":null,"startTime":299.576,"endTime":301.236,"body":"relation to other nuclepphiles."},{"speaker":null,"startTime":301.256,"endTime":304.886,"body":"So they have nucleophile A hasa value of one nucleophile B"},{"speaker":null,"startTime":304.886,"endTime":306.416,"body":"has a value of two and so on."},{"speaker":null,"startTime":306.836,"endTime":308.516,"body":"And so it is a logarithmic scale."},{"speaker":null,"startTime":308.606,"endTime":312.386,"body":"So the higher the value, the muchstronger than nucleophile and reacts."},{"speaker":null,"startTime":312.466,"endTime":312.556,"body":"But."},{"speaker":null,"startTime":313.036,"endTime":317.836,"body":"To have this useful as a tool inorganic synthesis, you have basically"},{"speaker":null,"startTime":317.836,"endTime":323.986,"body":"a nucleophile with a value of fivereacts in a fast manner- so seconds"},{"speaker":null,"startTime":323.986,"endTime":327.796,"body":"to minutes- with a Nu Electrophilewith the value of minus five."},{"speaker":null,"startTime":329.026,"endTime":333.286,"body":"So basically you just compare values andif the values are similar, you will get"},{"speaker":null,"startTime":333.286,"endTime":338.406,"body":"a reaction that is in controlled manner,but in a quick and good time scale."},{"speaker":null,"startTime":339.876,"endTime":347.166,"body":"This is actually where the critical pointof the Mayr scale is you have nucleophiles"},{"speaker":null,"startTime":347.186,"endTime":353.253,"body":"just range arranged by the strength, andso you can just see if an electrophile"},{"speaker":null,"startTime":353.253,"endTime":356.493,"body":"already got characterized or if aNucle valve already got characterized."},{"speaker":null,"startTime":357.003,"endTime":361.413,"body":"You can already see do they reactwith each other and do they react?"},{"speaker":null,"startTime":361.413,"endTime":363.753,"body":"So in a. Good timely manner."},{"speaker":null,"startTime":363.843,"endTime":363.933,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":364.383,"endTime":368.373,"body":"Justus: As a chemist, you don't want towait for a reaction for a month to finish."},{"speaker":null,"startTime":368.373,"endTime":368.433,"body":"Yeah."},{"speaker":null,"startTime":369.033,"endTime":371.763,"body":"But also it cannot, uh, react to fast."},{"speaker":null,"startTime":371.793,"endTime":375.543,"body":"'cause otherwise you are in the timelimit of the diffusion range basically."},{"speaker":null,"startTime":375.663,"endTime":380.583,"body":"And diffusion time limit range, alwaysmeans you have a loss of selectivity."},{"speaker":null,"startTime":380.588,"endTime":380.778,"body":"Mm-hmm."},{"speaker":null,"startTime":382.623,"endTime":384.753,"body":"Kevin: To determine and selectivity."},{"speaker":null,"startTime":384.753,"endTime":390.033,"body":"If you have two sides and then youwant to use these values to predict."},{"speaker":null,"startTime":390.528,"endTime":394.778,"body":"Which site is attacked by the nucleophile."},{"speaker":null,"startTime":395.448,"endTime":395.898,"body":"Justus: Yes."},{"speaker":null,"startTime":396.138,"endTime":398.958,"body":"So they are in the diffusion range."},{"speaker":null,"startTime":398.988,"endTime":400.518,"body":"You basically don't have control over."},{"speaker":null,"startTime":400.548,"endTime":400.638,"body":"Mm-hmm."},{"speaker":null,"startTime":400.878,"endTime":404.238,"body":"Because diffusion range means basicallyyou don't have a kinetic barrier."},{"speaker":null,"startTime":404.538,"endTime":404.628,"body":"Mm-hmm."},{"speaker":null,"startTime":405.168,"endTime":408.408,"body":"Meaning as soon as two moleculesmeet, prefer, preferably,"},{"speaker":null,"startTime":408.408,"endTime":410.628,"body":"they react and not just."},{"speaker":null,"startTime":410.943,"endTime":412.203,"body":"At one site."},{"speaker":null,"startTime":412.258,"endTime":412.578,"body":"Specifically."},{"speaker":null,"startTime":412.718,"endTime":413.138,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":413.273,"endTime":418.943,"body":"Justus: And so that the Mayr group, oralso now the Ofial group could do this"},{"speaker":null,"startTime":418.943,"endTime":426.323,"body":"whole nucleophilicity scale means one,uh, one very simple thing, the whole HSAB"},{"speaker":null,"startTime":426.473,"endTime":431.243,"body":"concept, and this also they describedas a paper, as I mentioned, is just."},{"speaker":null,"startTime":431.753,"endTime":433.253,"body":"Well, not really usable."},{"speaker":null,"startTime":433.313,"endTime":438.953,"body":"It is non, not sensible to use, and alot of chemists in their studies and"},{"speaker":null,"startTime":438.983,"endTime":443.638,"body":"also a lot of organic books in chemistrystill talk about the HSAB concept."},{"speaker":null,"startTime":443.638,"endTime":443.998,"body":"Mm-hmm."},{"speaker":null,"startTime":444.218,"endTime":449.303,"body":"As a concept you can refer to, you look atan embedded nucleophile like cyanide ion,"},{"speaker":null,"startTime":450.023,"endTime":457.353,"body":"and then you can say, okay, the cyanideion will react with hard electrophiles."},{"speaker":null,"startTime":457.613,"endTime":462.623,"body":"With the nitrogen site and with softelectro files with the, uh, carbon site,"},{"speaker":null,"startTime":462.623,"endTime":466.038,"body":"because you have in the cyanide ion,you have the electron rich nitrogen."},{"speaker":null,"startTime":466.533,"endTime":470.013,"body":"Which would be the hard siteaccording to the HSAB concept."},{"speaker":null,"startTime":470.403,"endTime":472.323,"body":"And you have the softerside with the carbon."},{"speaker":null,"startTime":472.803,"endTime":472.893,"body":"Mm-hmm."},{"speaker":null,"startTime":473.193,"endTime":473.613,"body":"Atom."},{"speaker":null,"startTime":474.453,"endTime":479.643,"body":"And according to the HSAB concept,depending on the electrophile, whether"},{"speaker":null,"startTime":479.643,"endTime":483.603,"body":"you have a hard electrophile or a softelectrophile, you would gather either get"},{"speaker":null,"startTime":483.603,"endTime":485.793,"body":"an nitrogen attack or a carbon attack."},{"speaker":null,"startTime":485.913,"endTime":486.003,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":486.753,"endTime":490.803,"body":"Justus: Now the nucleophilicity ofthe Mayr scale has one nucleophile"},{"speaker":null,"startTime":490.803,"endTime":492.453,"body":"strength for each nucleophile."},{"speaker":null,"startTime":493.263,"endTime":499.083,"body":"Saying this concept should not existif the Mayr scale is really valid,"},{"speaker":null,"startTime":500.643,"endTime":502.833,"body":"Kevin: the concept of that it has two."},{"speaker":null,"startTime":503.703,"endTime":505.173,"body":"Justus: The concept of HSAB."},{"speaker":null,"startTime":505.173,"endTime":505.383,"body":"Yeah."},{"speaker":null,"startTime":505.398,"endTime":505.558,"body":"Yeah."},{"speaker":null,"startTime":505.563,"endTime":505.573,"body":"Okay."},{"speaker":null,"startTime":505.623,"endTime":507.747,"body":"That you can basically uh,choose an electrophile."},{"speaker":null,"startTime":507.986,"endTime":511.976,"body":"It reacts with the nuclear or thenucleophile reacts with the electrophile,"},{"speaker":null,"startTime":512.576,"endTime":516.416,"body":"depending on the nucleophile site,whether the electrophile is hard or soft."},{"speaker":null,"startTime":516.421,"endTime":516.791,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":517.451,"endTime":520.961,"body":"Justus: So this whole HSAB conceptby Pearson that was developed mm-hmm."},{"speaker":null,"startTime":521.561,"endTime":525.041,"body":"Is just not a concept you canuse because it is not valid."},{"speaker":null,"startTime":525.191,"endTime":527.891,"body":"This is the claim that the Mayr Group did."},{"speaker":null,"startTime":528.071,"endTime":528.161,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":529.091,"endTime":534.221,"body":"Justus: And they also have, well, theyhave good reasons for this because if"},{"speaker":null,"startTime":534.341,"endTime":539.171,"body":"you look into literature and if youalso look at the examples and so on, you"},{"speaker":null,"startTime":539.171,"endTime":543.131,"body":"can actually see that the HSAB concept."},{"speaker":null,"startTime":543.776,"endTime":546.386,"body":"Doesn't hold true as a predictive tool."},{"speaker":null,"startTime":546.566,"endTime":546.686,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":546.986,"endTime":547.946,"body":"Justus: As a predictive tool."},{"speaker":null,"startTime":547.946,"endTime":550.796,"body":"It would be very strong in organicchemistry because you could actually"},{"speaker":null,"startTime":550.796,"endTime":556.286,"body":"use this for reactions and can say, if Idesign my nucleophile differently, I can"},{"speaker":null,"startTime":556.286,"endTime":558.626,"body":"use this as a tool to construct molecules."},{"speaker":null,"startTime":558.656,"endTime":558.746,"body":"Mm-hmm."},{"speaker":null,"startTime":559.136,"endTime":561.116,"body":"But actually it just doesn't hold true."},{"speaker":null,"startTime":561.236,"endTime":561.416,"body":"Kevin: Right."},{"speaker":null,"startTime":561.926,"endTime":566.156,"body":"I think the, the good part or thewhy it is so appealing to use this"},{"speaker":null,"startTime":566.156,"endTime":573.281,"body":"concept is because it is relativelyeasy to just look at the molecule and"},{"speaker":null,"startTime":573.281,"endTime":580.751,"body":"then see if this is a hard or a softnucleophile or um, acid, and you don't"},{"speaker":null,"startTime":580.751,"endTime":583.661,"body":"need to go to the lab and measure stuff."},{"speaker":null,"startTime":584.231,"endTime":586.121,"body":"Uh, from theory, obviously."},{"speaker":null,"startTime":586.121,"endTime":592.901,"body":"You have to then validate it and , andthat's where the limits, uh, came out."},{"speaker":null,"startTime":593.441,"endTime":593.861,"body":"But."},{"speaker":null,"startTime":595.091,"endTime":599.111,"body":"As a concept is, it's very appealingto just look at the molecules and be"},{"speaker":null,"startTime":599.111,"endTime":600.791,"body":"like, okay, this should react with this."},{"speaker":null,"startTime":600.791,"endTime":603.161,"body":"And then we go to the lab"},{"speaker":null,"startTime":603.161,"endTime":603.491,"body":"Justus: definitely."},{"speaker":null,"startTime":603.941,"endTime":606.281,"body":"I mean, that's also whyit's used and taught."},{"speaker":null,"startTime":606.951,"endTime":613.401,"body":"I mean a lot of students, and as I saidalso nowadays, up to date, newly coming"},{"speaker":null,"startTime":613.401,"endTime":618.621,"body":"out organic chemistry books still sellthe HSAB concept as something that is."},{"speaker":null,"startTime":619.391,"endTime":626.501,"body":"Of high value and that helps you predictor, uh, reaction outcomes, but well."},{"speaker":null,"startTime":627.201,"endTime":631.911,"body":"It just doesn't work out as it isexplained because this whole concept"},{"speaker":null,"startTime":631.911,"endTime":635.931,"body":"was designed somewhere in 1960s, Ithink 68 or something by Pearson."},{"speaker":null,"startTime":636.141,"endTime":638.991,"body":"And of course there were alsopredecessors, like Kornblume's rule rule,"},{"speaker":null,"startTime":638.991,"endTime":643.701,"body":"which stated, um, that uh, dependingon the transition state, you can"},{"speaker":null,"startTime":643.701,"endTime":645.351,"body":"determine the reaction outcome and so on."},{"speaker":null,"startTime":645.561,"endTime":648.561,"body":"And of course there's alalways some sense to it."},{"speaker":null,"startTime":648.741,"endTime":654.681,"body":"And that's also why it's so nice becauseif you can break down a model to really."},{"speaker":null,"startTime":655.041,"endTime":658.041,"body":"Really simple thingsand it still holds true."},{"speaker":null,"startTime":658.311,"endTime":658.401,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":659.211,"endTime":663.051,"body":"Justus: That's what well chemistsare looking for with every model for"},{"speaker":null,"startTime":663.051,"endTime":664.971,"body":"explaining students how chemistry works."},{"speaker":null,"startTime":664.971,"endTime":665.346,"body":"Kevin: Yeah, exactly."},{"speaker":null,"startTime":665.566,"endTime":667.746,"body":"Justus: But the problemis that basically all the."},{"speaker":null,"startTime":669.531,"endTime":674.541,"body":"All the examples that were made toprove the HSAB concept are either"},{"speaker":null,"startTime":674.541,"endTime":676.251,"body":"in the diffusion limit range."},{"speaker":null,"startTime":676.311,"endTime":676.401,"body":"Mm-hmm."},{"speaker":null,"startTime":676.641,"endTime":681.041,"body":"So you actually get also the otherattacking product not because the HSAB"},{"speaker":null,"startTime":681.041,"endTime":684.971,"body":"concept hold true, but you basicallyalways get mixtures in these cases."},{"speaker":null,"startTime":685.001,"endTime":687.431,"body":"Or you can just in the other thing."},{"speaker":null,"startTime":687.491,"endTime":688.451,"body":"Uh, in the other case."},{"speaker":null,"startTime":688.456,"endTime":690.016,"body":"Isolate kinetic products."},{"speaker":null,"startTime":690.016,"endTime":694.576,"body":"So it's not about the side hard andsoft, it's about thermodynamic or"},{"speaker":null,"startTime":694.576,"endTime":696.136,"body":"kinetic control of the reaction."},{"speaker":null,"startTime":696.436,"endTime":696.526,"body":"Mm-hmm."},{"speaker":null,"startTime":696.766,"endTime":702.166,"body":"And so this claim that is made,whether that the HSAB concept, hard"},{"speaker":null,"startTime":702.256,"endTime":706.606,"body":"reacts with hard and soft react tosoft well, could just not be proven?"},{"speaker":null,"startTime":706.606,"endTime":706.786,"body":"No."},{"speaker":null,"startTime":706.816,"endTime":710.626,"body":"Or more or less, it could beproven wrong by the group."},{"speaker":null,"startTime":711.286,"endTime":711.496,"body":"Kevin: Yeah."},{"speaker":null,"startTime":711.521,"endTime":717.021,"body":"All the models we use to explainwhat happens in chemistry are."},{"speaker":null,"startTime":718.271,"endTime":721.691,"body":"Always not like the exact reality."},{"speaker":null,"startTime":721.691,"endTime":726.391,"body":"They always just show or makethe reactions more visible."},{"speaker":null,"startTime":726.391,"endTime":731.341,"body":"And these models just hold upuntil someone proves them wrong."},{"speaker":null,"startTime":731.341,"endTime":736.041,"body":"And then we have a new model inthis case, then this, uh, Mayr"},{"speaker":null,"startTime":736.261,"endTime":744.841,"body":"scale, which, um, categorizes theelectrophiles and gives them values."},{"speaker":null,"startTime":745.381,"endTime":747.621,"body":"How fast they react with the nucleophiles?"},{"speaker":null,"startTime":748.141,"endTime":751.661,"body":"Justus: Well, they startbasically with the nucleophiles."},{"speaker":null,"startTime":751.681,"endTime":756.601,"body":"So, uh, there are over a thousandnucleophiles, I think now sorted"},{"speaker":null,"startTime":756.601,"endTime":760.531,"body":"in this and about, uh, I, I wouldneed to look up the numbers."},{"speaker":null,"startTime":760.531,"endTime":762.661,"body":"I think 200, 300 electrofiles or something."},{"speaker":null,"startTime":762.726,"endTime":767.046,"body":"So the nucleophile is a main reactingspecies is the focus on this."},{"speaker":null,"startTime":767.086,"endTime":771.496,"body":"it also got a nickname of, orit is more the principle of the"},{"speaker":null,"startTime":771.496,"endTime":774.106,"body":"constant selectivity relationship."},{"speaker":null,"startTime":774.136,"endTime":774.226,"body":"Kevin: Mm-hmm"},{"speaker":null,"startTime":774.616,"endTime":778.876,"body":"Justus: so you basically have anucleophile, it has a reacting"},{"speaker":null,"startTime":778.876,"endTime":780.016,"body":"site, and it has a strength."},{"speaker":null,"startTime":780.016,"endTime":780.826,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":780.832,"endTime":783.946,"body":"Justus: And either it reacts with anelectrophile or it doesn't react with the"},{"speaker":null,"startTime":783.946,"endTime":787.426,"body":"electrophile, depending on whether it'sstrong or whether it's weak or whatever."},{"speaker":null,"startTime":787.726,"endTime":787.906,"body":"Mm-hmm."},{"speaker":null,"startTime":788.146,"endTime":790.786,"body":"But it does not react on twodifferent sites, depending on."},{"speaker":null,"startTime":791.191,"endTime":794.311,"body":"Well, uh, so the nucleophile doesn'treact with two different sides of"},{"speaker":null,"startTime":794.311,"endTime":800.051,"body":"the atom, with the, of the moleculejust because, well, just because the"},{"speaker":null,"startTime":800.081,"endTime":801.311,"body":"electrophile behaves differently."},{"speaker":null,"startTime":801.341,"endTime":801.551,"body":"Yeah."},{"speaker":null,"startTime":801.581,"endTime":806.441,"body":"But, so it has one reactive siteand you can control still kinetic"},{"speaker":null,"startTime":806.441,"endTime":811.151,"body":"and thermodynamic or something,but you cannot have two different"},{"speaker":null,"startTime":811.181,"endTime":814.891,"body":"thermodynamic outcomes just becauseyou have a different electrophile."},{"speaker":null,"startTime":815.366,"endTime":815.786,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":817.301,"endTime":817.361,"body":"So."},{"speaker":null,"startTime":817.451,"endTime":822.521,"body":"It really focuses on if thereaction happens, but you can still"},{"speaker":null,"startTime":823.001,"endTime":829.781,"body":"also apply kinetic, um, controlto the reaction when you Yeah,"},{"speaker":null,"startTime":830.201,"endTime":836.021,"body":"Justus: I mean the, this is simply anotherchemistry model, whether you have a"},{"speaker":null,"startTime":836.021,"endTime":838.601,"body":"thermodynamic reaction or a kinetic, um."},{"speaker":null,"startTime":839.216,"endTime":840.356,"body":"Determine reaction."},{"speaker":null,"startTime":840.596,"endTime":844.586,"body":"This is something completely differentfrom that, but that's also one of"},{"speaker":null,"startTime":844.586,"endTime":846.356,"body":"the problems of the HSAB concept."},{"speaker":null,"startTime":846.686,"endTime":851.426,"body":"The HSAB concept never spokeabout kinetic or thermodynamic"},{"speaker":null,"startTime":851.426,"endTime":852.776,"body":"control or something like this."},{"speaker":null,"startTime":852.806,"endTime":852.896,"body":"Mm-hmm."},{"speaker":null,"startTime":853.136,"endTime":857.036,"body":"It just stated very simply,and also again in relation to"},{"speaker":null,"startTime":857.036,"endTime":859.826,"body":"Kornblume's rule, basically that you."},{"speaker":null,"startTime":860.561,"endTime":865.781,"body":"Have different interactions basedon hard and soft and also like"},{"speaker":null,"startTime":865.781,"endTime":867.376,"body":"orbital control versus mm-hmm."},{"speaker":null,"startTime":867.636,"endTime":869.021,"body":"Uh, coulomb control and so on."},{"speaker":null,"startTime":869.021,"endTime":873.881,"body":"But you basically have differentpoints of interaction depending on"},{"speaker":null,"startTime":873.941,"endTime":880.631,"body":"both reaction partners and, well,this is just as a general rule and"},{"speaker":null,"startTime":880.631,"endTime":886.451,"body":"as a concept you can use to predictreaction outcomes, just not usable."},{"speaker":null,"startTime":886.476,"endTime":886.896,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":887.686,"endTime":887.976,"body":"Yeah."},{"speaker":null,"startTime":888.036,"endTime":889.456,"body":"But now also with this."},{"speaker":null,"startTime":890.236,"endTime":895.816,"body":"Mayr scale where they actually havemeasured all these, nucleophiles"},{"speaker":null,"startTime":895.836,"endTime":898.806,"body":"and then give a strength to it."},{"speaker":null,"startTime":899.496,"endTime":901.896,"body":"You can relatively easy."},{"speaker":null,"startTime":901.896,"endTime":903.966,"body":"I've, uh, been on their website."},{"speaker":null,"startTime":903.966,"endTime":908.856,"body":"You can just look up, uh, moleculesand then see how, how strong they are."},{"speaker":null,"startTime":909.246,"endTime":914.826,"body":"Um, I guess also you could guess from."},{"speaker":null,"startTime":915.816,"endTime":919.776,"body":"One molecule to another if they're verysimilar but not the exact molecules"},{"speaker":null,"startTime":919.776,"endTime":921.096,"body":"in the scale that you could say."},{"speaker":null,"startTime":921.096,"endTime":921.336,"body":"Okay."},{"speaker":null,"startTime":921.336,"endTime":923.916,"body":"They should have a similar even."},{"speaker":null,"startTime":923.916,"endTime":924.456,"body":"Yeah, definitely."},{"speaker":null,"startTime":924.456,"endTime":928.986,"body":"Principally cover much more than there is,but there are already a lot of molecules."},{"speaker":null,"startTime":929.766,"endTime":933.696,"body":"Justus: Yeah, that definitely, I mean,of course you always have different."},{"speaker":null,"startTime":934.461,"endTime":936.501,"body":"Factors, determining,nucleophilicity and so on."},{"speaker":null,"startTime":936.921,"endTime":943.881,"body":"But then you also always can really lookat the basics of nucleophilicity, like"},{"speaker":null,"startTime":943.881,"endTime":945.791,"body":"what is nucleophilicity determined by?"},{"speaker":null,"startTime":945.851,"endTime":947.291,"body":"Uh, and that is very simple."},{"speaker":null,"startTime":947.291,"endTime":948.671,"body":"Do you have electron pushing groups?"},{"speaker":null,"startTime":948.671,"endTime":950.861,"body":"Do you have, uh, reaction center that is."},{"speaker":null,"startTime":951.596,"endTime":952.706,"body":"Freely available."},{"speaker":null,"startTime":952.706,"endTime":954.686,"body":"So no, uh, steric hindrance."},{"speaker":null,"startTime":955.076,"endTime":958.856,"body":"Uh, do you have an alpha effector, uh, directly attached"},{"speaker":null,"startTime":958.856,"endTime":960.716,"body":"to the nucleophilic atom?"},{"speaker":null,"startTime":960.776,"endTime":964.256,"body":"Do you have a atom attachedthat can donate a pi electron"},{"speaker":null,"startTime":964.256,"endTime":965.306,"body":"pair or something like this?"},{"speaker":null,"startTime":965.306,"endTime":966.596,"body":"And so, so."},{"speaker":null,"startTime":966.986,"endTime":972.506,"body":"You can always think about similarmolecules and then argue, okay,"},{"speaker":null,"startTime":972.746,"endTime":975.596,"body":"this is not measured, but thiscould have a stronger or a little"},{"speaker":null,"startTime":975.596,"endTime":978.776,"body":"bit weaker nucleophilicity,but it should be in this range."},{"speaker":null,"startTime":978.956,"endTime":979.046,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":979.286,"endTime":983.636,"body":"Justus: And that's why I think thenucleophilicity scale as a tool for"},{"speaker":null,"startTime":983.636,"endTime":985.196,"body":"chemist can be actually very strong."},{"speaker":null,"startTime":985.316,"endTime":985.406,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":985.646,"endTime":992.666,"body":"Do you have, uh, maybe some examples fromyour research when you use this scale to"},{"speaker":null,"startTime":992.726,"endTime":994.586,"body":"determine the outcome of a reaction or."},{"speaker":null,"startTime":995.636,"endTime":999.806,"body":"Justus: Um, so actually not to determinethe outcome of reaction, but in my"},{"speaker":null,"startTime":999.806,"endTime":1005.416,"body":"case, so I dealt with the instablemolecules and how to make them stable"},{"speaker":null,"startTime":1005.416,"endTime":1007.756,"body":"and so on during my PhD. Mm-hmm."},{"speaker":null,"startTime":1007.996,"endTime":1010.516,"body":"And the Hansmann group had the."},{"speaker":null,"startTime":1010.966,"endTime":1011.266,"body":"Yeah."},{"speaker":null,"startTime":1011.296,"endTime":1011.896,"body":"Also luck."},{"speaker":null,"startTime":1011.896,"endTime":1017.066,"body":"But we, we were able to show thestabilization of a new functional"},{"speaker":null,"startTime":1017.066,"endTime":1018.056,"body":"group in organic chemistry."},{"speaker":null,"startTime":1018.056,"endTime":1018.146,"body":"Mm-hmm."},{"speaker":null,"startTime":1018.806,"endTime":1020.756,"body":"And this doesn't happen everyday anymore since, yeah."},{"speaker":null,"startTime":1020.756,"endTime":1022.196,"body":"Kevin: That's, that's rare."},{"speaker":null,"startTime":1022.286,"endTime":1024.266,"body":"Justus: Most functionalgroups are already known."},{"speaker":null,"startTime":1024.266,"endTime":1027.996,"body":"But in 2021, we were the firstones to report stable diazoalkenes."},{"speaker":null,"startTime":1028.016,"endTime":1028.676,"body":"Mm-hmm."},{"speaker":null,"startTime":1029.246,"endTime":1036.401,"body":"The diazoalkanes, so basically just CNtwo ties are known for, I think 1880"},{"speaker":null,"startTime":1036.401,"endTime":1040.901,"body":"or something like this, so they'reknown for over a hundred years, and"},{"speaker":null,"startTime":1040.931,"endTime":1043.331,"body":"well-established group with mm-hmm."},{"speaker":null,"startTime":1043.661,"endTime":1044.861,"body":"Reactivity explored in everything."},{"speaker":null,"startTime":1045.491,"endTime":1049.431,"body":"The diazoalenes, sojust the higher homolog."},{"speaker":null,"startTime":1049.451,"endTime":1049.452,"body":"Mm-hmm."},{"speaker":null,"startTime":1049.453,"endTime":1049.991,"body":"C, C N two."},{"speaker":null,"startTime":1050.041,"endTime":1053.191,"body":"Well, they have been proposed asintermediates in a lot of organic"},{"speaker":null,"startTime":1053.191,"endTime":1058.561,"body":"reactions actually, and they, sothey are potentially a useful group"},{"speaker":null,"startTime":1058.561,"endTime":1060.361,"body":"also to use as an organic chemist."},{"speaker":null,"startTime":1060.991,"endTime":1067.021,"body":"But up to 19, uh, I don'tknow, I don't remember."},{"speaker":null,"startTime":1067.021,"endTime":1071.221,"body":"19 80, 19 90, something likethis, they couldn't even be proven"},{"speaker":null,"startTime":1071.221,"endTime":1072.841,"body":"in matrix isolation studies."},{"speaker":null,"startTime":1073.216,"endTime":1079.456,"body":"And Matrix isolation studies are studiesthat basically try to isolate really"},{"speaker":null,"startTime":1079.456,"endTime":1082.546,"body":"single molecules in a frozen argon matrix."},{"speaker":null,"startTime":1083.116,"endTime":1088.426,"body":"So molecules at around fiveKelvin, three Kelvin depends, 10"},{"speaker":null,"startTime":1088.426,"endTime":1089.456,"body":"Kelvin depends on the reactions."},{"speaker":null,"startTime":1089.506,"endTime":1096.256,"body":"But you really try to deposit moleculessingle handedly by vacuum methods."},{"speaker":null,"startTime":1097.156,"endTime":1103.696,"body":"Onto a surface and then try to coolthem down to very, very low temperatures"},{"speaker":null,"startTime":1103.696,"endTime":1105.766,"body":"Kevin: so they don't move anymore."},{"speaker":null,"startTime":1105.766,"endTime":1108.796,"body":"And there there's no not enoughenergy in the system that they"},{"speaker":null,"startTime":1108.796,"endTime":1110.536,"body":"react with anything and then you can"},{"speaker":null,"startTime":1110.626,"endTime":1111.106,"body":"Justus: Exactly."},{"speaker":null,"startTime":1111.226,"endTime":1112.876,"body":"And they are completely singled out."},{"speaker":null,"startTime":1112.876,"endTime":1115.456,"body":"So they also cannot dimerizeeasily or whatsoever."},{"speaker":null,"startTime":1116.416,"endTime":1120.886,"body":"Well, that is the ideal theorybehind this, but, so you can"},{"speaker":null,"startTime":1120.886,"endTime":1124.666,"body":"really research the most highlyreactive intermediates and whatnot."},{"speaker":null,"startTime":1125.476,"endTime":1133.236,"body":"But up to this point, actually evenwell, attempts to, uh, study diazoalkene"},{"speaker":null,"startTime":1133.606,"endTime":1135.626,"body":"s in this method didn't work."},{"speaker":null,"startTime":1135.926,"endTime":1135.986,"body":"Yeah,"},{"speaker":null,"startTime":1136.646,"endTime":1140.336,"body":"Kevin: because they were tooreactive and even at this, uh, low"},{"speaker":null,"startTime":1140.336,"endTime":1141.806,"body":"temperature, they did something."},{"speaker":null,"startTime":1141.906,"endTime":1144.306,"body":"Justus: So they startedto intramolecular stuff."},{"speaker":null,"startTime":1144.306,"endTime":1147.606,"body":"And even at these temperatures,you have to imagine even this is"},{"speaker":null,"startTime":1147.606,"endTime":1150.696,"body":"difficult for molecules to do becauseyou still have to have degrees of"},{"speaker":null,"startTime":1150.696,"endTime":1152.046,"body":"freedom and rotation and so on."},{"speaker":null,"startTime":1152.526,"endTime":1158.796,"body":"And this, well, Matrixx isolationis for suppressing these things."},{"speaker":null,"startTime":1159.156,"endTime":1164.376,"body":"But it took until then to provethe first, diazoalkene which well."},{"speaker":null,"startTime":1164.901,"endTime":1167.061,"body":"In the matrix isolationstudy was impossible."},{"speaker":null,"startTime":1167.241,"endTime":1167.331,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1167.841,"endTime":1169.401,"body":"Justus: But you couldn't stabilize them."},{"speaker":null,"startTime":1169.491,"endTime":1174.561,"body":"And then 2021, we were able to,well synthesize first that are"},{"speaker":null,"startTime":1174.561,"endTime":1177.591,"body":"stable even at room temperatureand solution, and even over days."},{"speaker":null,"startTime":1178.791,"endTime":1184.941,"body":"Kevin: Okay and how could you stabilizethem with the construction of the molecule"},{"speaker":null,"startTime":1184.941,"endTime":1188.541,"body":"that only certain diazoalkenes are stable?"},{"speaker":null,"startTime":1188.541,"endTime":1192.951,"body":"Or did you have a method toactually stabilize all of them?"},{"speaker":null,"startTime":1193.341,"endTime":1198.721,"body":"Justus: Um, well, at the first it wasjust a lucky shot, but, basically it was"},{"speaker":null,"startTime":1198.721,"endTime":1204.631,"body":"done with super strong nuclophiles, andthis was done by, with the reaction of"},{"speaker":null,"startTime":1204.741,"endTime":1209.491,"body":"N2O, which is super strong nucleophiles,so well nitrous oxide, laughing gas."},{"speaker":null,"startTime":1210.001,"endTime":1217.921,"body":"Um, the thing about this super strongnucleophiles is that N2O is normally a"},{"speaker":null,"startTime":1217.921,"endTime":1223.691,"body":"rather inert gas or, if it reacts, it isknown to react basically under N2 release."},{"speaker":null,"startTime":1223.721,"endTime":1224.981,"body":"So it oxidizes stuff."},{"speaker":null,"startTime":1225.011,"endTime":1225.101,"body":"Mm-hmm."},{"speaker":null,"startTime":1225.341,"endTime":1226.241,"body":"And N2 is released."},{"speaker":null,"startTime":1226.241,"endTime":1229.601,"body":"And this is of course,thermodynamically super much favored."},{"speaker":null,"startTime":1229.601,"endTime":1229.661,"body":"Yeah."},{"speaker":null,"startTime":1230.291,"endTime":1233.881,"body":"But, uh, these very,very strong nucleophiles."},{"speaker":null,"startTime":1234.281,"endTime":1237.171,"body":"They're called mesoionicN-heterocyclic olefines."},{"speaker":null,"startTime":1237.191,"endTime":1241.841,"body":"Uh, but it's basically just apolarization of a carbon atom so"},{"speaker":null,"startTime":1241.841,"endTime":1247.601,"body":"far that it's basically has ananioid character more or less."},{"speaker":null,"startTime":1247.601,"endTime":1251.711,"body":"And this could then react, uh,with N2O in a fashion that it"},{"speaker":null,"startTime":1251.711,"endTime":1254.221,"body":"attacks the nitrogen atom of N2O"},{"speaker":null,"startTime":1255.131,"endTime":1260.081,"body":"Kevin: and then there is no nitrogenrelease in, in direction because that's,"},{"speaker":null,"startTime":1260.501,"endTime":1262.331,"body":"that's targeted by the equivalent"},{"speaker":null,"startTime":1262.331,"endTime":1263.411,"body":"Justus: bond formation point."},{"speaker":null,"startTime":1263.861,"endTime":1268.961,"body":"And so in the end, uh, actually wateris just released in the, well, in"},{"speaker":null,"startTime":1268.961,"endTime":1271.121,"body":"a multiple step reaction process."},{"speaker":null,"startTime":1271.121,"endTime":1271.341,"body":"But."},{"speaker":null,"startTime":1272.466,"endTime":1276.766,"body":"You had the ability here to usethese super strong nucleophiles."},{"speaker":null,"startTime":1277.256,"endTime":1284.066,"body":"And that's why I meant we didn't,I didn't use in my PhD to, uh, this"},{"speaker":null,"startTime":1284.066,"endTime":1288.326,"body":"nucleophilicity scale to predictoutcomes, but we actually tried to"},{"speaker":null,"startTime":1288.326,"endTime":1290.246,"body":"then manipulate a little bit or tryout."},{"speaker":null,"startTime":1291.761,"endTime":1294.371,"body":"How strong does Nuclide really need to be?"},{"speaker":null,"startTime":1294.401,"endTime":1297.406,"body":"We worked there with the Ofialgroup now to get, mm-hmm."},{"speaker":null,"startTime":1297.611,"endTime":1300.881,"body":"In collaboration to determinethe nucleis and so on."},{"speaker":null,"startTime":1301.331,"endTime":1306.701,"body":"And then we just, well took lessand less nucleic uh, molecules to"},{"speaker":null,"startTime":1306.701,"endTime":1310.991,"body":"see how strong does nucleophilehave to be to react with N2O."},{"speaker":null,"startTime":1311.006,"endTime":1311.366,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1311.451,"endTime":1315.371,"body":"Justus: And then also whyis the diazoalkene, stable?"},{"speaker":null,"startTime":1315.371,"endTime":1319.241,"body":"Well, actually they are stableas a group because these."},{"speaker":null,"startTime":1320.156,"endTime":1328.256,"body":"The precursors, the reagents mesoionicolefins, uh, donate super much electron"},{"speaker":null,"startTime":1328.256,"endTime":1332.366,"body":"density into the CN two fragmentinto this diazoalkene fragment."},{"speaker":null,"startTime":1332.756,"endTime":1332.846,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1332.936,"endTime":1335.996,"body":"Justus: So that it's actually stablybound to the rest of the molecule."},{"speaker":null,"startTime":1336.386,"endTime":1340.526,"body":"And the lower you go in electron densitythat is pushed into this fragment,"},{"speaker":null,"startTime":1340.916,"endTime":1342.806,"body":"the more unstable this becomes."},{"speaker":null,"startTime":1343.256,"endTime":1346.646,"body":"And so we actually played around withthis nucleophilicity scale and really had."},{"speaker":null,"startTime":1347.486,"endTime":1351.206,"body":"Values we could attend to ofdifferent olefines where we could"},{"speaker":null,"startTime":1351.206,"endTime":1354.476,"body":"see, okay, this gets less andless stable because less electron"},{"speaker":null,"startTime":1354.476,"endTime":1356.096,"body":"density is pushed into the fragment."},{"speaker":null,"startTime":1356.126,"endTime":1356.246,"body":"Mm-hmm."},{"speaker":null,"startTime":1356.766,"endTime":1361.926,"body":"Kevin: The more nuclear lic, uh,compound is, the more electron it"},{"speaker":null,"startTime":1361.926,"endTime":1369.096,"body":"gives to the, uh, molecule and themore electron density you have in this."},{"speaker":null,"startTime":1369.471,"endTime":1373.011,"body":"Uh, molecule, the more stable it becomes."},{"speaker":null,"startTime":1373.671,"endTime":1373.881,"body":"Justus: Yeah."},{"speaker":null,"startTime":1374.241,"endTime":1381.128,"body":"Kevin: So when you have lower and lowernucleophilic strengths, then you have"},{"speaker":null,"startTime":1381.128,"endTime":1388.628,"body":"lower and lower electron donation to thisreaction, and then it becomes less stable."},{"speaker":null,"startTime":1389.648,"endTime":1389.918,"body":"Justus: Well, it's."},{"speaker":null,"startTime":1391.043,"endTime":1394.943,"body":"You cannot use this as a general concept,just push electron density into something"},{"speaker":null,"startTime":1394.943,"endTime":1396.173,"body":"and then it becomes more stable."},{"speaker":null,"startTime":1396.353,"endTime":1400.943,"body":"But in the case of diazoalkene,we could see that, well, basically"},{"speaker":null,"startTime":1400.943,"endTime":1406.913,"body":"this holds true in a, as ageneral rule of thumb, basically."},{"speaker":null,"startTime":1407.243,"endTime":1414.543,"body":"Um, but this is also due to theelectronic situation of the diazoalkene."},{"speaker":null,"startTime":1414.773,"endTime":1419.288,"body":"They diazoalkene are in stablegenerally as a group because they"},{"speaker":null,"startTime":1419.288,"endTime":1421.268,"body":"are very easy also to lose nitrogen."},{"speaker":null,"startTime":1421.478,"endTime":1425.058,"body":"So di nitrogen eliminationagain to build a diradical."},{"speaker":null,"startTime":1425.078,"endTime":1425.498,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1426.008,"endTime":1429.248,"body":"Justus: And it's a little bitmore complicated again, about"},{"speaker":null,"startTime":1429.248,"endTime":1433.568,"body":"Clet and triplet state, which westudied then also and basically"},{"speaker":null,"startTime":1433.928,"endTime":1436.388,"body":"Kevin: of the, um, radical"},{"speaker":null,"startTime":1436.508,"endTime":1436.988,"body":"Justus: Yes."},{"speaker":null,"startTime":1437.078,"endTime":1438.008,"body":"Yeah, exactly."},{"speaker":null,"startTime":1438.488,"endTime":1444.158,"body":"Um, if you push more electron densityinto this fragment instead of the."},{"speaker":null,"startTime":1445.058,"endTime":1448.868,"body":"Singlet, state of theinstable diazoalkene, you get"},{"speaker":null,"startTime":1448.868,"endTime":1450.128,"body":"suddenly, a triplet state."},{"speaker":null,"startTime":1450.728,"endTime":1455.988,"body":"And there you can see that basicallythe, again, just the nucleophilicity"},{"speaker":null,"startTime":1456.008,"endTime":1457.538,"body":"of the precursor, you could say."},{"speaker":null,"startTime":1457.538,"endTime":1462.128,"body":"But in general, just the electrondonating rescue you put to your functional"},{"speaker":null,"startTime":1462.128,"endTime":1468.638,"body":"group, uh, stabilizes this moleculeand stabilizes the two loss that these"},{"speaker":null,"startTime":1468.638,"endTime":1472.448,"body":"molecules don't just loose into becauseit's so thermodynamically favored."},{"speaker":null,"startTime":1472.448,"endTime":1472.838,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1473.618,"endTime":1479.408,"body":"Justus: If the question, if thereis an electron, poor diazoalkene is"},{"speaker":null,"startTime":1479.408,"endTime":1484.868,"body":"another question and probably not, butmaybe there's a way to stabilize them."},{"speaker":null,"startTime":1484.868,"endTime":1487.388,"body":"But this we didn't manage so far."},{"speaker":null,"startTime":1487.448,"endTime":1488.408,"body":"We just could see."},{"speaker":null,"startTime":1488.468,"endTime":1494.318,"body":"Yeah, we just could see that basicallythe more nucleic the precursor is, so the"},{"speaker":null,"startTime":1494.318,"endTime":1498.878,"body":"more electron density it's able to donate,the more stable is the diazoalkene?"},{"speaker":null,"startTime":1498.973,"endTime":1499.393,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1499.718,"endTime":1504.038,"body":"So that, that's why you thenexplored the upper range of this"},{"speaker":null,"startTime":1504.038,"endTime":1506.338,"body":"Mayr scale of the Nu nucleophiles."},{"speaker":null,"startTime":1506.408,"endTime":1509.678,"body":"Justus: Yeah, actually this was alot of fun, but they're really just"},{"speaker":null,"startTime":1509.978,"endTime":1514.508,"body":"basic concepts of chemistry can beseen because we, after designing"},{"speaker":null,"startTime":1514.508,"endTime":1522.788,"body":"this m-NHOs, these olefines, uh, webasically tried to see how much can"},{"speaker":null,"startTime":1522.788,"endTime":1527.318,"body":"we push this bar, because with them-NHOs, we could already see they are."},{"speaker":null,"startTime":1527.978,"endTime":1532.478,"body":"Super strong nucleophilicis qualitative experiments."},{"speaker":null,"startTime":1532.718,"endTime":1535.743,"body":"We could see they are morenucleophilic, for example, than NHCs."},{"speaker":null,"startTime":1535.803,"endTime":1536.223,"body":"Mm-hmm."},{"speaker":null,"startTime":1536.308,"endTime":1539.258,"body":"Than the four just basic chemists."},{"speaker":null,"startTime":1539.258,"endTime":1541.728,"body":"Also known the theseN-heterocyclic carbens."},{"speaker":null,"startTime":1542.398,"endTime":1548.908,"body":"But these more niche functional rootof the N-heterocaclic olefines and"},{"speaker":null,"startTime":1548.998,"endTime":1552.268,"body":"also then the mesoionic olefines,which are even more polarized."},{"speaker":null,"startTime":1553.168,"endTime":1553.408,"body":"They are."},{"speaker":null,"startTime":1555.508,"endTime":1557.398,"body":"Is not much known about this."},{"speaker":null,"startTime":1557.428,"endTime":1561.988,"body":"And then we wanted to see what typesof influence can we use to really push"},{"speaker":null,"startTime":1561.988,"endTime":1564.358,"body":"the electron density on this fragment?"},{"speaker":null,"startTime":1564.358,"endTime":1566.748,"body":"And so thus also the nucleophilicity."},{"speaker":null,"startTime":1567.028,"endTime":1567.118,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1567.748,"endTime":1570.748,"body":"Justus: On the carbon atomas a nuclear flic center."},{"speaker":null,"startTime":1570.898,"endTime":1573.658,"body":"And also how far can we go?"},{"speaker":null,"startTime":1574.438,"endTime":1577.348,"body":"And this, how far can we go wasn'tactually very funny because it"},{"speaker":null,"startTime":1577.348,"endTime":1581.878,"body":"was the, it is now the strongestnucleophile reported up to date."},{"speaker":null,"startTime":1581.878,"endTime":1583.308,"body":"So the strongest nucleophile."},{"speaker":null,"startTime":1583.893,"endTime":1587.908,"body":"Known is a mesoionic olefinethat I designed during my"},{"speaker":null,"startTime":1587.908,"endTime":1589.768,"body":"PhD, which was very fun."},{"speaker":null,"startTime":1590.488,"endTime":1594.478,"body":"Kevin: That sounds pretty amazing,especially when you have, uh, a"},{"speaker":null,"startTime":1594.478,"endTime":1597.388,"body":"new functional group to work with."},{"speaker":null,"startTime":1597.388,"endTime":1601.798,"body":"And then because of that yousee, okay, what else is possible?"},{"speaker":null,"startTime":1601.828,"endTime":1607.798,"body":"And then you, to test this new functionalgroup, you also push the limits of."},{"speaker":null,"startTime":1608.533,"endTime":1610.843,"body":"This nucleophilic scale that, yeah."},{"speaker":null,"startTime":1611.023,"endTime":1612.103,"body":"Sounds very interesting."},{"speaker":null,"startTime":1612.443,"endTime":1615.593,"body":"They're probably not, uh,directly, uh, applications of"},{"speaker":null,"startTime":1615.593,"endTime":1617.633,"body":"this chemistry yet, I assume."},{"speaker":null,"startTime":1618.023,"endTime":1623.693,"body":"But pushing the, the basic, uh,research in this field is then."},{"speaker":null,"startTime":1624.623,"endTime":1628.553,"body":"Yeah, basically gives a whole newbranch of, of chemistry in this or"},{"speaker":null,"startTime":1628.763,"endTime":1632.513,"body":"with the functional group, you coulddo a lot and it's not known yet."},{"speaker":null,"startTime":1632.843,"endTime":1633.263,"body":"Justus: Yeah."},{"speaker":null,"startTime":1633.323,"endTime":1637.973,"body":"So of course direct applicationsis always tricky with things like"},{"speaker":null,"startTime":1637.973,"endTime":1640.853,"body":"this because this is basic research."},{"speaker":null,"startTime":1640.853,"endTime":1646.283,"body":"Research really of basic concepts andof what can we actually do not with the"},{"speaker":null,"startTime":1646.283,"endTime":1648.653,"body":"main focus on what can we use it for."},{"speaker":null,"startTime":1648.863,"endTime":1648.953,"body":"Mm-hmm."},{"speaker":null,"startTime":1649.193,"endTime":1652.793,"body":"And so I would say, ofcourse, if you have a new."},{"speaker":null,"startTime":1653.258,"endTime":1656.918,"body":"Functional group and organic chemistry,that's very, very useful because you"},{"speaker":null,"startTime":1656.918,"endTime":1661.538,"body":"can have, again, basically an additionaltool as a organic chemist to design"},{"speaker":null,"startTime":1661.538,"endTime":1663.638,"body":"molecules and how to construct molecules."},{"speaker":null,"startTime":1664.388,"endTime":1669.172,"body":"But even if you apply this toinstable diazoalkene because we"},{"speaker":null,"startTime":1669.172,"endTime":1672.742,"body":"were able to isolate diazoalkeneand research the reactivity and so"},{"speaker":null,"startTime":1672.742,"endTime":1677.632,"body":"on, we could really just much morefocused and much more controlled."},{"speaker":null,"startTime":1678.202,"endTime":1679.072,"body":"See and."},{"speaker":null,"startTime":1680.047,"endTime":1685.517,"body":"Um, isolate the products of reactionsof the diazoalkenes with some educts."},{"speaker":null,"startTime":1686.087,"endTime":1693.257,"body":"And so we could see that thdiazoalkenengswith carbon monoxide react to the, uh,"},{"speaker":null,"startTime":1693.257,"endTime":1697.727,"body":"ketens and so and so just reactionsthat were before, not really able to"},{"speaker":null,"startTime":1697.727,"endTime":1699.437,"body":"do this in controlled manner and so on."},{"speaker":null,"startTime":1699.827,"endTime":1702.717,"body":"We could now see and reactedwith different electrophiles"},{"speaker":null,"startTime":1702.737,"endTime":1703.607,"body":"what the outcome is."},{"speaker":null,"startTime":1703.622,"endTime":1704.972,"body":"Kevin: Hmm, interesting."},{"speaker":null,"startTime":1704.972,"endTime":1710.552,"body":"Justus: And if you now would synthesizeinstable, the akins, you could maybe"},{"speaker":null,"startTime":1710.552,"endTime":1714.422,"body":"use this as a tool in your reaction set."},{"speaker":null,"startTime":1714.422,"endTime":1719.562,"body":"So you don't even need to use thesevery special, stabilized, diazoalkenes,"},{"speaker":null,"startTime":1719.582,"endTime":1721.412,"body":"but you can use this as a general tool."},{"speaker":null,"startTime":1721.892,"endTime":1722.102,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1722.102,"endTime":1728.252,"body":"Because you learned from the stableones, there are not that many, but"},{"speaker":null,"startTime":1728.612,"endTime":1733.412,"body":"because they're stable, you canlook into the reactions much better."},{"speaker":null,"startTime":1733.787,"endTime":1736.667,"body":"Understand how thisfunctional group works."},{"speaker":null,"startTime":1736.667,"endTime":1744.257,"body":"And then you have these instable ones,which were previously just, yeah, they,"},{"speaker":null,"startTime":1744.257,"endTime":1750.107,"body":"they might be there as an, uh, transitionstate, but could not really be proven."},{"speaker":null,"startTime":1750.467,"endTime":1755.627,"body":"And now where you predict thatthis, diazoalkene will be as a"},{"speaker":null,"startTime":1755.627,"endTime":1759.887,"body":"transition state, you can use whatyou learned from the stable ones to."},{"speaker":null,"startTime":1761.252,"endTime":1765.422,"body":"Yeah, predict what happens withthese, or at least understand better"},{"speaker":null,"startTime":1765.422,"endTime":1767.952,"body":"how these transition steps work."},{"speaker":null,"startTime":1768.462,"endTime":1769.452,"body":"Justus: Yeah, exactly."},{"speaker":null,"startTime":1769.602,"endTime":1772.962,"body":"And thus, for example, one ofthe projects that was really"},{"speaker":null,"startTime":1772.962,"endTime":1775.002,"body":"cool was also we were able to."},{"speaker":null,"startTime":1775.707,"endTime":1778.527,"body":"Incorporation with the Kasanmascheffgroup, also at the tear dorm,"},{"speaker":null,"startTime":1778.527,"endTime":1781.497,"body":"but they have an EPR spectrum."},{"speaker":null,"startTime":1781.497,"endTime":1788.067,"body":"So basically they could research thistriplet species that results, uh, after"},{"speaker":null,"startTime":1788.067,"endTime":1794.847,"body":"the N2 loss when if you radiate with lightand they research this species and could"},{"speaker":null,"startTime":1794.907,"endTime":1797.487,"body":"see the first triplet vinyliden formed."},{"speaker":null,"startTime":1797.697,"endTime":1797.787,"body":"Mm-hmm."},{"speaker":null,"startTime":1798.027,"endTime":1802.027,"body":"So the first CC fragmentwhere there's a diradical."},{"speaker":null,"startTime":1802.137,"endTime":1802.197,"body":"Hm."},{"speaker":null,"startTime":1802.677,"endTime":1804.177,"body":"In the triplet state."},{"speaker":null,"startTime":1804.327,"endTime":1811.197,"body":"And so because of this basic research,we were able to analyze, characterize,"},{"speaker":null,"startTime":1811.197,"endTime":1814.822,"body":"and also a little bit play around withspecies that were before not known."},{"speaker":null,"startTime":1814.822,"endTime":1815.182,"body":"Mm-hmm."},{"speaker":null,"startTime":1815.362,"endTime":1818.967,"body":"And also could not be characterizedbecause of the instability."},{"speaker":null,"startTime":1818.972,"endTime":1819.142,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":1819.747,"endTime":1823.947,"body":"Justus: And thus this basicresearch doesn't have a"},{"speaker":null,"startTime":1824.127,"endTime":1825.777,"body":"direct focus on application."},{"speaker":null,"startTime":1825.777,"endTime":1830.427,"body":"It also doesn't have any directconnection right now, but there's some"},{"speaker":null,"startTime":1830.427,"endTime":1832.527,"body":"basic research that can be built upon."},{"speaker":null,"startTime":1832.767,"endTime":1832.917,"body":"Kevin: Yeah."},{"speaker":null,"startTime":1833.127,"endTime":1841.317,"body":"And, and it pushes the models thatwe know to a limit and helps to"},{"speaker":null,"startTime":1841.377,"endTime":1846.807,"body":"refine these models to make themmore generally, applicable and."},{"speaker":null,"startTime":1847.947,"endTime":1854.247,"body":"Yeah, it's really interesting when yougo really so, so deep into the basics"},{"speaker":null,"startTime":1854.247,"endTime":1859.347,"body":"of chemistry that you still can findnew stuff and it's not, yeah, we have"},{"speaker":null,"startTime":1859.407,"endTime":1865.872,"body":"research chemistry for so many years that,uh, now all the basic concepts known and"},{"speaker":null,"startTime":1865.872,"endTime":1868.767,"body":"we just have to find new applications."},{"speaker":null,"startTime":1868.767,"endTime":1873.117,"body":"No, we actually can still findnew functional groups, new models."},{"speaker":null,"startTime":1873.237,"endTime":1874.707,"body":"That's, yeah, pretty amazing."},{"speaker":null,"startTime":1875.982,"endTime":1876.252,"body":"Justus: Yeah,"},{"speaker":null,"startTime":1876.372,"endTime":1881.292,"body":"actually I think that's the whole baseor the whole reason for basic chemist"},{"speaker":null,"startTime":1881.352,"endTime":1884.982,"body":"or base basic research, why this isstill important and why this should"},{"speaker":null,"startTime":1884.982,"endTime":1890.172,"body":"still be also focused on it, not onlydirectly with a focus on applications,"},{"speaker":null,"startTime":1890.172,"endTime":1892.692,"body":"but can we push this further?"},{"speaker":null,"startTime":1892.692,"endTime":1893.982,"body":"Can we actually do something here?"},{"speaker":null,"startTime":1893.982,"endTime":1895.182,"body":"And of course, in."},{"speaker":null,"startTime":1895.572,"endTime":1900.222,"body":"The eyes of application focusedchemists or application focused people."},{"speaker":null,"startTime":1900.312,"endTime":1900.522,"body":"Yeah."},{"speaker":null,"startTime":1900.522,"endTime":1903.852,"body":"This maybe a little bit just, yeah,playing around and with no real"},{"speaker":null,"startTime":1903.852,"endTime":1906.402,"body":"target or so on and in my eyes,"},{"speaker":null,"startTime":1906.402,"endTime":1906.732,"body":"Kevin: yet."},{"speaker":null,"startTime":1907.182,"endTime":1912.342,"body":"That's the thing that it, itwill eventually, someone wants"},{"speaker":null,"startTime":1912.342,"endTime":1913.722,"body":"this concept is established."},{"speaker":null,"startTime":1913.722,"endTime":1917.292,"body":"Someone will use it in adifferent way because they're"},{"speaker":null,"startTime":1917.292,"endTime":1920.742,"body":"not focused on how stuff work."},{"speaker":null,"startTime":1920.742,"endTime":1922.782,"body":"They are then focused on."},{"speaker":null,"startTime":1923.142,"endTime":1924.522,"body":"Okay, we have this new concept."},{"speaker":null,"startTime":1924.522,"endTime":1925.842,"body":"Now how can we apply it?"},{"speaker":null,"startTime":1926.052,"endTime":1929.562,"body":"But to apply it first we have tounderstand how it works, and that's"},{"speaker":null,"startTime":1930.162,"endTime":1931.722,"body":"why we need this kind of research."},{"speaker":null,"startTime":1932.472,"endTime":1933.312,"body":"Yeah, definitely."},{"speaker":null,"startTime":1933.312,"endTime":1939.132,"body":"When you see more, then you can canlook into new stuff that was just."},{"speaker":null,"startTime":1940.287,"endTime":1946.257,"body":"Not possible to see anymore, I think, uh,before the electron was uh, discovered."},{"speaker":null,"startTime":1946.257,"endTime":1953.637,"body":"And it's just, just like, uh,that's very drastic, uh, finding."},{"speaker":null,"startTime":1953.637,"endTime":1959.787,"body":"But um, before that it was also notknown that there are smaller particles."},{"speaker":null,"startTime":1959.787,"endTime":1966.477,"body":"And then this opened basically up thewhole research about also in chemistry"},{"speaker":null,"startTime":1966.657,"endTime":1972.057,"body":"on how these electrons are placed inthe molecules and how they are basically"},{"speaker":null,"startTime":1972.057,"endTime":1976.557,"body":"the, the, uh, way how molecules interact."},{"speaker":null,"startTime":1977.187,"endTime":1977.577,"body":"Justus: Yeah."},{"speaker":null,"startTime":1977.627,"endTime":1981.677,"body":"Of course you cannot make every daythese groundbreaking discoveries,"},{"speaker":null,"startTime":1982.097,"endTime":1983.987,"body":"which is a little bit sad, but yeah."},{"speaker":null,"startTime":1984.317,"endTime":1987.677,"body":"Uh, for example, for the nucleophilicitymeasurements that I did together"},{"speaker":null,"startTime":1987.677,"endTime":1992.117,"body":"with the Ofial group and so on, itwas also, and actually still some"},{"speaker":null,"startTime":1992.117,"endTime":1995.867,"body":"papers you can find where it statesthe nucleophilicity can, can be just"},{"speaker":null,"startTime":1995.867,"endTime":1998.717,"body":"correlated, for example, to the protonaffinity or something like this."},{"speaker":null,"startTime":1998.717,"endTime":1998.807,"body":"Mm-hmm."},{"speaker":null,"startTime":1999.047,"endTime":2001.387,"body":"And proton affinities youcan really easily calculate"},{"speaker":null,"startTime":2001.727,"endTime":2004.637,"body":"Kevin: proton affinity means howwell they react with protons."},{"speaker":null,"startTime":2004.817,"endTime":2005.267,"body":"Justus: Uh, yeah."},{"speaker":null,"startTime":2005.267,"endTime":2009.797,"body":"Basically it's uh, how well youcan take up a proton or a little"},{"speaker":null,"startTime":2009.797,"endTime":2012.167,"body":"bit simpler expressed the basicity."},{"speaker":null,"startTime":2012.167,"endTime":2017.462,"body":"It's not exactly the same, but basicallyI. A lot of papers still state, you"},{"speaker":null,"startTime":2017.462,"endTime":2021.302,"body":"can correlate the nucleophilicityand the basicity of molecules."},{"speaker":null,"startTime":2021.357,"endTime":2027.507,"body":"And while this holds true for simplermolecules and can give you a general"},{"speaker":null,"startTime":2027.507,"endTime":2032.037,"body":"idea, maybe this is just not it."},{"speaker":null,"startTime":2032.037,"endTime":2036.967,"body":"It's not a general correlationbecause the big difference between"},{"speaker":null,"startTime":2037.057,"endTime":2039.577,"body":"a general electrophile and a proton."},{"speaker":null,"startTime":2040.357,"endTime":2042.187,"body":"Is the proton is super small."},{"speaker":null,"startTime":2042.367,"endTime":2042.457,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2042.697,"endTime":2046.027,"body":"Justus: And the orbital situationis super easy to understand."},{"speaker":null,"startTime":2046.507,"endTime":2050.227,"body":"For electrophiles, this iscompletely different because electro"},{"speaker":null,"startTime":2050.227,"endTime":2054.337,"body":"files then have an electrophiliccenter in organic chemistry."},{"speaker":null,"startTime":2054.337,"endTime":2057.247,"body":"Of course, a lot of carbonelectrophilic centers."},{"speaker":null,"startTime":2057.327,"endTime":2058.887,"body":"But these have different geometries."},{"speaker":null,"startTime":2058.887,"endTime":2062.817,"body":"These have different, uh, energyvalues generally speaking."},{"speaker":null,"startTime":2063.147,"endTime":2068.007,"body":"And so if you're attacking this,also the reorganization in during"},{"speaker":null,"startTime":2068.007,"endTime":2072.917,"body":"the process, takes a lot of, wellplay, uh, influence on the whole"},{"speaker":null,"startTime":2072.977,"endTime":2074.687,"body":"energetic profile of the reaction."},{"speaker":null,"startTime":2075.587,"endTime":2082.037,"body":"And so, for example, just researchingthese m-NHOs and how you can influence"},{"speaker":null,"startTime":2082.042,"endTime":2086.387,"body":"the nucleophilicity in the systemsgives you a good understanding of"},{"speaker":null,"startTime":2086.387,"endTime":2090.767,"body":"how you can influence nucleophilicityalso, generally speaking more broadly"},{"speaker":null,"startTime":2090.767,"endTime":2094.757,"body":"on the, on the Heterocyclic core."},{"speaker":null,"startTime":2094.787,"endTime":2095.027,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2096.272,"endTime":2101.112,"body":"Justus: And if you now just say thenucleophilicity can be correlated"},{"speaker":null,"startTime":2101.112,"endTime":2107.052,"body":"to the, uh, proton affinity, this isjust a rough measure that will fail"},{"speaker":null,"startTime":2107.052,"endTime":2111.882,"body":"if you really look for designingspecifically hetero cycles with different"},{"speaker":null,"startTime":2111.882,"endTime":2113.712,"body":"electron density due distributions."},{"speaker":null,"startTime":2114.392,"endTime":2114.602,"body":"Kevin: Why?"},{"speaker":null,"startTime":2116.402,"endTime":2120.952,"body":"Justus: Really easily speaking, if youhave the carbon atom as a nucleophile."},{"speaker":null,"startTime":2121.182,"endTime":2122.202,"body":"Attacking a proton."},{"speaker":null,"startTime":2123.087,"endTime":2127.977,"body":"The proton will not reorganize itsstructure because of just one atom."},{"speaker":null,"startTime":2129.147,"endTime":2133.887,"body":"And also it doesn't matterwhich nucleophile you have."},{"speaker":null,"startTime":2134.187,"endTime":2140.247,"body":"The proton will always be just assimple S orbital thing where you attack"},{"speaker":null,"startTime":2140.427,"endTime":2144.927,"body":"into, and if you are talking about the."},{"speaker":null,"startTime":2145.507,"endTime":2148.797,"body":"electrophiles, like carbon,electrophiles, nitrogen, electrophiles,"},{"speaker":null,"startTime":2148.812,"endTime":2152.232,"body":"may, maybe, or something likethis, like imines or something."},{"speaker":null,"startTime":2152.232,"endTime":2152.382,"body":"Mm-hmm."},{"speaker":null,"startTime":2153.342,"endTime":2154.932,"body":"It's, it's very, very simple."},{"speaker":null,"startTime":2155.292,"endTime":2159.492,"body":"You have, um, electrophilic core."},{"speaker":null,"startTime":2160.077,"endTime":2161.907,"body":"But of course you have molecular orbitals."},{"speaker":null,"startTime":2161.967,"endTime":2162.117,"body":"Yeah."},{"speaker":null,"startTime":2162.507,"endTime":2166.077,"body":"And you have molecular structuresof these electrophiles and if not"},{"speaker":null,"startTime":2166.077,"endTime":2168.927,"body":"the nucleophile attacks, you have areorganization of the whole molecule."},{"speaker":null,"startTime":2169.107,"endTime":2169.197,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2169.587,"endTime":2172.407,"body":"Justus: And you have steric hindrancein these partners and so on."},{"speaker":null,"startTime":2172.857,"endTime":2176.487,"body":"And you have orbital overlaps thatfirst need to happen for the reaction"},{"speaker":null,"startTime":2176.817,"endTime":2178.467,"body":"to, for the equivalent bond form."},{"speaker":null,"startTime":2179.037,"endTime":2179.487,"body":"And"},{"speaker":null,"startTime":2179.547,"endTime":2181.857,"body":"Kevin: they have to match previously."},{"speaker":null,"startTime":2181.857,"endTime":2182.037,"body":"So."},{"speaker":null,"startTime":2182.652,"endTime":2186.342,"body":"That you cannot react anyorbital with any orbital."},{"speaker":null,"startTime":2186.882,"endTime":2187.152,"body":"Justus: Exactly."},{"speaker":null,"startTime":2187.152,"endTime":2189.822,"body":"Kevin: But when there'sonly one, it's, yeah."},{"speaker":null,"startTime":2190.362,"endTime":2192.672,"body":"Justus: Reacting witha proton is no problem."},{"speaker":null,"startTime":2192.672,"endTime":2196.152,"body":"And you basically cannot make sterichindrance, arguments or whatever."},{"speaker":null,"startTime":2196.752,"endTime":2200.232,"body":"And this, we could also seesteric hindrance is a big,"},{"speaker":null,"startTime":2200.232,"endTime":2201.732,"body":"big factor in nucleophilicity."},{"speaker":null,"startTime":2202.092,"endTime":2202.662,"body":"How."},{"speaker":null,"startTime":2203.037,"endTime":2208.437,"body":"Well, or in, well some cases andhow badly your reaction center is"},{"speaker":null,"startTime":2208.437,"endTime":2214.287,"body":"really protected by or shielded byother organic rests or something."},{"speaker":null,"startTime":2214.287,"endTime":2214.377,"body":"Mm-hmm."},{"speaker":null,"startTime":2215.072,"endTime":2216.442,"body":"Hinders, of course, reaction."},{"speaker":null,"startTime":2216.447,"endTime":2216.507,"body":"Mm-hmm."},{"speaker":null,"startTime":2217.557,"endTime":2221.277,"body":"And so the nucleophilicity willgrow lower and lower because,"},{"speaker":null,"startTime":2221.487,"endTime":2226.227,"body":"well, how do you stabilize somevery reactive intermediates?"},{"speaker":null,"startTime":2226.677,"endTime":2228.537,"body":"Just put a lot of bulk around them."},{"speaker":null,"startTime":2229.467,"endTime":2236.727,"body":"Kevin: So it's, uh, like when you usedye isopropyl amide, where it is, uh, nu"},{"speaker":null,"startTime":2236.727,"endTime":2240.177,"body":"nucleophile, but because of its shielding."},{"speaker":null,"startTime":2240.387,"endTime":2241.977,"body":"It's, yeah."},{"speaker":null,"startTime":2242.007,"endTime":2247.397,"body":"Basically can only react as a nucleophile."},{"speaker":null,"startTime":2247.647,"endTime":2248.607,"body":"No, it's a strong"},{"speaker":null,"startTime":2248.607,"endTime":2249.237,"body":"Justus: Its a base."},{"speaker":null,"startTime":2249.327,"endTime":2249.807,"body":"Kevin: Yeah."},{"speaker":null,"startTime":2249.807,"endTime":2250.287,"body":"As a base."},{"speaker":null,"startTime":2250.287,"endTime":2250.557,"body":"Yeah."},{"speaker":null,"startTime":2250.707,"endTime":2252.027,"body":"No, but I mix this up."},{"speaker":null,"startTime":2252.027,"endTime":2253.767,"body":"But this is, it is theother way around, right?"},{"speaker":null,"startTime":2253.767,"endTime":2253.857,"body":"Yeah."},{"speaker":null,"startTime":2253.857,"endTime":2254.367,"body":"But actually,"},{"speaker":null,"startTime":2254.427,"endTime":2255.147,"body":"Justus: yeah, exactly."},{"speaker":null,"startTime":2255.147,"endTime":2260.247,"body":"This is, uh, very important point in, Imean, generally also in organic chemistry."},{"speaker":null,"startTime":2260.277,"endTime":2260.727,"body":"Why you have."},{"speaker":null,"startTime":2261.627,"endTime":2263.737,"body":"Non nucleic strong bases."},{"speaker":null,"startTime":2263.847,"endTime":2263.937,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2263.937,"endTime":2263.997,"body":"Yeah,"},{"speaker":null,"startTime":2264.297,"endTime":2266.517,"body":"Justus: because sometimes youreally just want the base character."},{"speaker":null,"startTime":2266.517,"endTime":2269.427,"body":"You just want a reactionwhere you remove a proton."},{"speaker":null,"startTime":2270.027,"endTime":2274.177,"body":"But if you at the same time havenucleophile, a lot of electrophiles"},{"speaker":null,"startTime":2274.197,"endTime":2278.707,"body":"can also, of course, so theycannot only react as electrophiles,"},{"speaker":null,"startTime":2278.727,"endTime":2280.917,"body":"they can also react as acids."},{"speaker":null,"startTime":2281.017,"endTime":2285.667,"body":"Kevin: You, but that was, was that alsoa problem with your, uh, compounds?"},{"speaker":null,"startTime":2286.057,"endTime":2287.947,"body":"From what I remember, they were also."},{"speaker":null,"startTime":2288.982,"endTime":2292.352,"body":"Strong nucleophile, butdon't really react as bases."},{"speaker":null,"startTime":2292.462,"endTime":2294.022,"body":"Justus: I mean, oh,they're super strong base."},{"speaker":null,"startTime":2294.802,"endTime":2296.812,"body":"They're definitely,they're super strong base."},{"speaker":null,"startTime":2296.812,"endTime":2302.212,"body":"But, uh, well that's one of the partswhy they are, for example, air sensitive"},{"speaker":null,"startTime":2302.572,"endTime":2307.612,"body":"with in air, they immediately erect withwater and also oxygen for that matter."},{"speaker":null,"startTime":2307.662,"endTime":2311.382,"body":"Basically the separation of Nucle,Felicity, and Basicity is very"},{"speaker":null,"startTime":2311.382,"endTime":2315.102,"body":"important because you need to knowwhen this is a super strong base."},{"speaker":null,"startTime":2315.162,"endTime":2315.252,"body":"Mm-hmm."},{"speaker":null,"startTime":2315.492,"endTime":2318.222,"body":"And calculating protonaffinity is super easy."},{"speaker":null,"startTime":2319.182,"endTime":2322.722,"body":"You cannot say, okay, this isa strong nucleophile, and you"},{"speaker":null,"startTime":2322.722,"endTime":2325.932,"body":"can also say, this is a strongernucleophile, or is this a stronger"},{"speaker":null,"startTime":2325.932,"endTime":2327.797,"body":"base, which reacts first, and so on."},{"speaker":null,"startTime":2327.797,"endTime":2328.037,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2328.482,"endTime":2333.552,"body":"Justus: Of course, base if it's has ahigh basicity, uh, the reaction with."},{"speaker":null,"startTime":2333.837,"endTime":2338.847,"body":"Protons is always just kineticallyvery preferred just because a"},{"speaker":null,"startTime":2338.847,"endTime":2343.257,"body":"proton is so small and can justtransport much faster and so on."},{"speaker":null,"startTime":2343.587,"endTime":2347.907,"body":"But that's also why we thendid calculations with methyl"},{"speaker":null,"startTime":2347.907,"endTime":2353.787,"body":"cation, uh, affinities andmethyl cat, just the CH3 plus."},{"speaker":null,"startTime":2354.357,"endTime":2358.137,"body":"Still a very simple molecule andstill for nowadays computers."},{"speaker":null,"startTime":2358.722,"endTime":2363.132,"body":"Relatively easy to calculate,uh, the reaction between any"},{"speaker":null,"startTime":2363.132,"endTime":2364.622,"body":"nucleophile and the methyl cation."},{"speaker":null,"startTime":2365.372,"endTime":2369.282,"body":"The methyl cation affinities, you canactually much more closely correlate"},{"speaker":null,"startTime":2369.282,"endTime":2370.812,"body":"to the nucle felicities mm-hmm."},{"speaker":null,"startTime":2370.812,"endTime":2372.642,"body":"While the proton affinities fail there."},{"speaker":null,"startTime":2373.182,"endTime":2373.403,"body":"Kevin: Oh, okay."},{"speaker":null,"startTime":2373.917,"endTime":2377.277,"body":"Justus: But, so doing these studies,seeing how we can influence the"},{"speaker":null,"startTime":2377.277,"endTime":2382.227,"body":"nucleophilicity, we then also try toapply this for computational methods,"},{"speaker":null,"startTime":2382.227,"endTime":2385.617,"body":"and there we could see the correlationto the proton affinities fails."},{"speaker":null,"startTime":2385.707,"endTime":2385.827,"body":"Yeah."},{"speaker":null,"startTime":2385.917,"endTime":2389.847,"body":"While a simple calculation of themethyl cation affinities gives you"},{"speaker":null,"startTime":2389.847,"endTime":2393.417,"body":"a very good picture, actually ofwhat the nucleophilicity should be."},{"speaker":null,"startTime":2393.747,"endTime":2393.837,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2395.067,"endTime":2399.747,"body":"Yeah, that's also a good pointthat you have to see how these"},{"speaker":null,"startTime":2399.747,"endTime":2401.307,"body":"different concepts then work."},{"speaker":null,"startTime":2402.267,"endTime":2408.357,"body":"Um, maybe one questionin a different direction."},{"speaker":null,"startTime":2408.417,"endTime":2416.397,"body":"So when you started with your researchand you had this very new, uh, functional"},{"speaker":null,"startTime":2416.397,"endTime":2423.717,"body":"group, how did you start with, like,did you just want to play around with"},{"speaker":null,"startTime":2423.717,"endTime":2428.157,"body":"it and see what happens or what wasthe, the target when you started?"},{"speaker":null,"startTime":2428.157,"endTime":2428.577,"body":"I know that."},{"speaker":null,"startTime":2429.417,"endTime":2432.777,"body":"Uh, in the PhD, sometimes you havea plan in the beginning and then"},{"speaker":null,"startTime":2433.497,"endTime":2437.907,"body":"you just at some point go in acompletely different directions."},{"speaker":null,"startTime":2438.807,"endTime":2440.637,"body":"How was this with your PhD?"},{"speaker":null,"startTime":2440.637,"endTime":2444.897,"body":"Justus: I had a, actually a completelydifferent plan for the PhD, uh,"},{"speaker":null,"startTime":2444.927,"endTime":2446.847,"body":"because I started in the group."},{"speaker":null,"startTime":2447.807,"endTime":2451.917,"body":"Then we discovered the, the diazoalkenesbut actually it was not me on the"},{"speaker":null,"startTime":2451.917,"endTime":2453.477,"body":"project who discovered this, but, uh."},{"speaker":null,"startTime":2453.837,"endTime":2458.967,"body":"Fellow, uh, PhD colleague, and thenI basically took over this topic and,"},{"speaker":null,"startTime":2460.227,"endTime":2467.457,"body":"uh, well, we started investigationsbasically by, first of all, what's known"},{"speaker":null,"startTime":2467.457,"endTime":2470.182,"body":"about diazoalkenes so diazoalkenes are."},{"speaker":null,"startTime":2471.217,"endTime":2475.387,"body":"Well, known is difficult, butthey were at least postulated."},{"speaker":null,"startTime":2475.442,"endTime":2476.492,"body":"In a lot of reactions."},{"speaker":null,"startTime":2476.492,"endTime":2479.102,"body":"And so of course you have alook, they're postulated here."},{"speaker":null,"startTime":2479.372,"endTime":2481.892,"body":"Can we use this and can wesee the same reactivity?"},{"speaker":null,"startTime":2482.252,"endTime":2485.912,"body":"Can we really talk about thesepostulated diazoalkenes in the same way?"},{"speaker":null,"startTime":2485.912,"endTime":2488.312,"body":"We couldn't talk about our stable akins."},{"speaker":null,"startTime":2488.342,"endTime":2488.432,"body":"Mm-hmm."},{"speaker":null,"startTime":2488.822,"endTime":2490.532,"body":"This was one of the first steps."},{"speaker":null,"startTime":2490.892,"endTime":2497.942,"body":"Then you of course look for, you have a.Novel functional group that is of, that"},{"speaker":null,"startTime":2497.942,"endTime":2502.952,"body":"seems to be very energy rich becausestill we are talking about a molecule that"},{"speaker":null,"startTime":2502.952,"endTime":2505.322,"body":"can easily activate stuff that we can."},{"speaker":null,"startTime":2505.532,"endTime":2510.962,"body":"So the mesoionic olefins, the precursorshave a very high nucleophilicity."},{"speaker":null,"startTime":2511.027,"endTime":2511.247,"body":"Kevin: Mm-hmm."},{"speaker":null,"startTime":2511.742,"endTime":2516.632,"body":"Justus: And that Akins should havestill a high nucleophilicity at least."},{"speaker":null,"startTime":2517.322,"endTime":2518.522,"body":"Uh, this we."},{"speaker":null,"startTime":2518.837,"endTime":2521.867,"body":"Also research, but this is notpublished now, but they are"},{"speaker":null,"startTime":2521.897,"endTime":2523.357,"body":"very, very strong nucleophiles."},{"speaker":null,"startTime":2523.997,"endTime":2530.717,"body":"And basically what we did wason the one hand, see, well"},{"speaker":null,"startTime":2530.717,"endTime":2535.297,"body":"similarities between postulateddiazoalkenes and our diazoalkenes."},{"speaker":null,"startTime":2535.697,"endTime":2537.407,"body":"But also we had a look."},{"speaker":null,"startTime":2537.407,"endTime":2540.977,"body":"Okay, uh, diazoalkanes, the homolog,"},{"speaker":null,"startTime":2540.977,"endTime":2541.337,"body":"Kevin: yeah."},{"speaker":null,"startTime":2541.547,"endTime":2542.272,"body":"Justus: Uh, has."},{"speaker":null,"startTime":2542.712,"endTime":2543.622,"body":"Known reactivity."},{"speaker":null,"startTime":2544.127,"endTime":2544.277,"body":"Mm-hmm."},{"speaker":null,"startTime":2544.367,"endTime":2548.147,"body":"And they are, of course, one of that'salso one of the first examples that was"},{"speaker":null,"startTime":2548.147,"endTime":2550.487,"body":"of course, trait diazoalkanes are known."},{"speaker":null,"startTime":2550.517,"endTime":2555.707,"body":"If you radiate them with wavelength400, 350 nanometers or something"},{"speaker":null,"startTime":2555.707,"endTime":2558.387,"body":"like this, or whatever, they lose N2."},{"speaker":null,"startTime":2558.737,"endTime":2560.227,"body":"Can we do the same with the diazoalkenes?"},{"speaker":null,"startTime":2560.357,"endTime":2561.407,"body":"Yes, of course we can."},{"speaker":null,"startTime":2561.467,"endTime":2562.037,"body":"What happens?"},{"speaker":null,"startTime":2562.037,"endTime":2562.457,"body":"And so on."},{"speaker":null,"startTime":2562.667,"endTime":2567.197,"body":"So the first thing you start fromis mostly things that are what"},{"speaker":null,"startTime":2567.197,"endTime":2568.222,"body":"they already are closely known,"},{"speaker":null,"startTime":2568.482,"endTime":2568.782,"body":"Kevin: and then."},{"speaker":null,"startTime":2569.642,"endTime":2573.362,"body":"You try to apply these conceptsand see if they still work."},{"speaker":null,"startTime":2573.362,"endTime":2574.232,"body":"Justus: Mm-hmm."},{"speaker":null,"startTime":2574.292,"endTime":2575.732,"body":"Kevin: And if not, why not?"},{"speaker":null,"startTime":2576.302,"endTime":2576.542,"body":"Justus: Mm-hmm."},{"speaker":null,"startTime":2576.932,"endTime":2577.772,"body":"If they still work."},{"speaker":null,"startTime":2577.772,"endTime":2582.092,"body":"And also, of course diazoalkeneswere not stable before this."},{"speaker":null,"startTime":2582.212,"endTime":2588.272,"body":"And then can we get to other closelyrelated, uh, molecules that are not stable"},{"speaker":null,"startTime":2588.272,"endTime":2592.847,"body":"and are they also then somehow stablewith the approach we chose and so on."},{"speaker":null,"startTime":2592.927,"endTime":2596.087,"body":"And there we also could see a lotof very interesting stuff, but"},{"speaker":null,"startTime":2596.177,"endTime":2596.417,"body":"Kevin: yeah."},{"speaker":null,"startTime":2596.417,"endTime":2596.477,"body":"Yeah."},{"speaker":null,"startTime":2597.377,"endTime":2598.457,"body":"Yeah, very interesting."},{"speaker":null,"startTime":2598.457,"endTime":2605.897,"body":"It's a topic where you have to really,uh, emphasize your curiosity and just"},{"speaker":null,"startTime":2607.037,"endTime":2610.157,"body":"go more deeply into this chemistry."},{"speaker":null,"startTime":2610.307,"endTime":2610.997,"body":"Very interesting."},{"speaker":null,"startTime":2610.997,"endTime":2611.357,"body":"Yeah."},{"speaker":null,"startTime":2611.687,"endTime":2615.917,"body":"Thank you for, uh, for the talk andit was very interesting to learn"},{"speaker":null,"startTime":2615.917,"endTime":2618.527,"body":"about these very basic concepts."},{"speaker":null,"startTime":2618.627,"endTime":2618.837,"body":"Justus: Yeah."},{"speaker":null,"startTime":2618.837,"endTime":2622.467,"body":"Thank you for giving me the chance to talkhere about my chemistry and what's nice."},{"speaker":null,"startTime":2622.867,"endTime":2628.357,"body":"Kevin: If you like this episode,please consider following on wherever"},{"speaker":null,"startTime":2628.777,"endTime":2630.667,"body":"you're listening to this podcast."},{"speaker":null,"startTime":2631.447,"endTime":2636.267,"body":"Also, you can find out moreon innovateandreact.com."},{"speaker":null,"startTime":2636.667,"endTime":2640.207,"body":"There you can find all the episodesand additional informations."},{"speaker":null,"startTime":2640.907,"endTime":2645.257,"body":"If you have an interesting topicthat you would like to share with"},{"speaker":null,"startTime":2645.257,"endTime":2652.612,"body":"the audience, contact me via emailcontact@innovateandreact.com or"},{"speaker":null,"startTime":2652.882,"endTime":2656.817,"body":"find me as Kevin Hares on LinkedIn."},{"speaker":null,"startTime":2658.022,"endTime":2661.262,"body":"Thank you so much forlistening and stay curious."}]}