Kinetics of alkylhalocarbene rearrangements: modulation by fluorine substituents

Moss, Robert A.; Ho, Guo Jie; Liu, Weiguo

doi:10.1021/ja00029a025

Cited by 48 publications

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“…84 Bob Moss and his co-workers had measured ΔH q = 3.6 kcal/mol and ΔS q = À22.5 eu for this reaction. 83 There is obviously a significant difference between the calculated and observed activation parameters for the rearrangement of 26 to 27.…”

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confidence: 96%

“…83 Clearly, there was and there still is a major disagreement between the results of Don's calculations and Bob's experiments because, to date, neither Don, nor Bob, nor I have been able to think of a way to reconcile the conflicting results.…”

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confidence: 97%

“…83 Barry Carpenter reminded me that Don Truhlar had created a program called POLYRATE for calculating rate constants with inclusion of corrections for multidimensional tunneling. Therefore, I asked Don if he was interested in carrying out POLYRATE calculations to see if tunneling was responsible for the low values of ΔH q and ΔS q that Bob Moss had measured for the ring expansion of 26.…”

Section: Don Truhlar Does More Calculations Bob Moss Does More Expermentioning

confidence: 99%

“…83 Professor Alan Goren was on sabbatical in my research group at the time, and when I returned from Hawaii, I asked him to do some (10/10)CASSCF and CASPT2 calculations on the ring expansion of fluorocyclopropylcarbene (26) to 1-fluorocyclobutene (27), one of the reactions that Bob had studied experimentally. Alan calculated ΔH q = 14.7 kcal/mol and ΔS q = À2.7 eu at the (10/10)CASPT2/cc-pVTZ//(10/10)CASSCF/6-31G* level of theory.…”

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With a Little Help from My Friends: Forty Years of Fruitful Chemical Collaborations

Borden

2011

J. Org. Chem.

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A former colleague of mine at the University of Washington once told me, only half-jokingly, "You do a lot of collaborative research, and I think the reason for its success is that you are brave enough to choose as your collaborators people who are better chemists than you." Looking back over the past 40 years of my career, I have, indeed, had an unusually large number of research collaborations, and they have, in fact, been successful, largely because my collaborators have all been talented chemists who had expertise that I lacked.These collaborations have come about in several ways. In some cases, an experimentalist has asked my research group to perform calculations. On other occasions, I have sought collaborators outside of my own research group when I needed help, usually experimental but sometimes computational, in testing a prediction. I have also had research collaborations begin when I was on sabbatical or when Professors from other universities spent sabbaticals in my research group, usually with the goal of learning how to do electronic structure calculations.This Perspective allows me to thank at least a few of my many collaborators over the past 40 years by recounting how their contributions made it possible for me to do research that I probably would not have been able to do on my own. This Perspective also gives me the opportunity to give some examples of the synergism between theory and experiments in my research and to acknowledge the important role that serendipity has played throughout my career, but particularly in the collaborative projects that are the focus of this Perspective. I have been lucky in having had puzzling experimental and computational results brought to my attention at times when I had the knowledge and/or computational resources that were necessary in order to explain those results. I have also been very fortunate in knowing experimentalists and theoreticians who were willing to collaborate with me on experiments and calculations that were of interest to me, but which I could not have readily done on my own.Serendipity has also played a different kind of role in my research. When I have been working on finding the solution to a specific problem, my research has frequently led me to the solution of a problem of much broader scope. I attribute my good fortune, at least in part, to my compulsive habit of persistently asking myself the question, "Why is that?" when I am presented with an experimental or computational result that I do not understand.I have divided this Perspective into eight major sections, each of which describes a different area of my research during the past 40 years, in which collaborations have played an important role. Rather than reading this Perspective in its entirety, some readers may prefer to be selective and peruse just a few of the eight sections. The sections cover my collaborative research on (1) hydrocarbons containing unsaturatively 1,3-bridged cyclobutane rings, (2) the use of orbital topology for predicting the ground states of diradicals, (3)...

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Section: Don Truhlar Does More Calculations Bob Moss Does More Expermentioning

confidence: 99%

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confidence: 99%

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With a Little Help from My Friends: Forty Years of Fruitful Chemical Collaborations

Borden

2011

J. Org. Chem.

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“…[1][2][3] This rearrangement has been shown to involve a hydride-like shift from neighboring carbons to the vacant carbene p-orbital. [4][5][6][7] Similarly, 1,2-migrations of other species such as alkyl, aryl, and halo groups, are believed to involve anion-like shifts from adjacent carbons to the vacant carbene p-orbital. 1 In contrast, 1,2-migrations from neighboring oxygens to the carbene carbon are quite rare and mechanistically more complex.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the mechanism of 1,2-migrations in methoxysiloxycarbene with the electron localization function

Loncke¹,

Gadosy²,

Peslherbe³

2002

Arkivoc

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A topological analysis of the gradient vector field of the electron localization function (ELF) has been used to investigate the mechanism of 1,2-silyl migration from oxygen to the carbene carbon in methoxysiloxycarbene. As well, the analogous 1,2-methyl migration was investigated for comparison. Plots of ELF isosurfaces and contour maps clearly reveal that the monosynaptic valence basin corresponding to the carbene lone pair becomes the disynaptic valence basin corresponding to the developing carbon-silicon bond in the transition state for 1,2-silyl migration, while it remains effectively unaltered in the transition state for 1,2-methyl migration. These results suggest that 1,2-silyl migration proceeds via nucleophilic attack by the carbene lone pair at silicon, whereas the energetically unfavorable 1,2-methyl migration appears to involve an anion-like shift from oxygen to the carbene center, in good agreement with previous findings.

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Tunneling in the Reactions of Carbenes and Oxacarbenes

Gerbig

Schreiner

2013

Contemporary Carbene Chemistry

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Kinetics of alkylhalocarbene rearrangements: modulation by fluorine substituents

Cited by 48 publications

References 0 publications

With a Little Help from My Friends: Forty Years of Fruitful Chemical Collaborations

With a Little Help from My Friends: Forty Years of Fruitful Chemical Collaborations

Investigation of the mechanism of 1,2-migrations in methoxysiloxycarbene with the electron localization function

Tunneling in the Reactions of Carbenes and Oxacarbenes

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