Absolute rate constants for additions of phenylchlorocarbene to alkenes

Turro, Nicholas J.; Butcher, Jared A.; Moss, Robert A.; Guo, Wenjeng; Munjal, Ramesh C.; Fedoryński, M.

doi:10.1021/ja00545a037

Cited by 62 publications

(37 citation statements)

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“…)2 laser spectroscopy allowed a direct test of the implied selectivity-reactivity relationship, because direct measurement of the absolute rate constants for reactions of carbenes became possible by this technique. The absolute rate constants for the reactions of PCC and some of its derivatives with tetramethylethylene (a relatively reactive olefin) and with 1-hexene (a relatively unreactive olefin) in isooctane have been determined (40)(41)(42). For even the most reactive systems, the rate constant (-1.5 x 109M-1 sec'1) is slightly below the diffusion control limit for isooctane (-1 x 10'0M-' sec-').…”

Section: Reactions Of Excited Triplet Carbenes With Alcoholsmentioning

confidence: 99%

Divalent Carbon Intermediates: Laser Photolysis and Spectroscopy

Eisenthal

Moss

Turro

1984

Science

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A brief review is given of the structures of an important class of reactive intermediates, divalent carbon species (carbenes). The electronic properties of carbenes force an unusual electronic character upon these species that, in turn, leads to intriguing physical and chemical properties. Because of the fleeting nature of carbenes, which are extraordinarily reactive, direct investigation of their structural and chemical behavior has presented a challenge to the experimentalist. The application of spectroscopic and ultrafast laser techniques has met this challenge. With the use of laser methods, along with conventional techniques, quantitative evaluation of the energetics, dynamics, and reactivities of a variety of carbenes has been possible.

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Section: Reactions Of Excited Triplet Carbenes With Alcoholsmentioning

confidence: 99%

Divalent Carbon Intermediates: Laser Photolysis and Spectroscopy

Eisenthal

Moss

Turro

1984

Science

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“…Within an hour, Nicks group had obtained the UV spectrum of singlet phenylchlorocarbene in solution at ambient temperature. [28] We did not know it, but Schusters group at the University of Illinois was simultaneously doing similar experiments with singlet and triplet fluorenylidene. [29] Our initial experiments paved the way for the determination of absolute rate constants for the reactions of many singlet carbenes with alkenes (and other substrates) under normal reaction conditions, and led to a delightful collaboration with Nick Turro, including several extended joint group seminars followed by luncheons at a nearby Greek restaurant aptly named The Symposium.…”

Section: Independent Researchmentioning

confidence: 99%

A Half‐Century Odyssey in the Realm of Reactive Intermediates

Moss

2015

Israel Journal of Chemistry

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Through a retrospective examination of the author’s half‐century immersion in physical organic chemistry, an attempt is made to identify some broader currents in the field. Among these are the cyclical nature of physical organic chemistry, the persistence of research themes, the driving force of new instrumentation, paradigm shifts in theory, greater computational power, enhanced time resolution of experiments, and the export of mechanism‐based analysis to other foci of contemporary science.

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“…[15b, 148,149] Similarly, no reaction with H 2 (by abstraction/recombination) in an H 2 -doped argon matrix was observed. [150] However, singlet carbene 54-Cl reacted slowly with 3 O 2 in a spin-forbidden pro-cess when it was photolytically generated in an argon matrix.…”

Section: Chloro(phenyl)carbenementioning

confidence: 99%

“…[68,153] The τ of carbene 54-Cl is reported to be around 3.6 µs (λ max = 310 nm; [154] 2,2,4-trimethylpentane), as determined by LFP of diazirine 55. [148,155] At T = 10 K, matrix-isolated 54-Cl completely undergoes ring expansion to 1-chloro-1,2,4,6-cycloheptatetraene (-63) when exposed to short wavelength irradiation (λ Ͼ 254 nm) (Scheme 17). Neither 7-chlorobicyclo[4.1.0]hepta-2,4,6-triene (64) nor 2-chloro-2,4,6-cycloheptatrien-1-ylidene (65) was observed during prolonged irradiation (λ Ͼ 338 nm) of carbene 54-Cl.…”

Section: Chloro(phenyl)carbenementioning

confidence: 99%

Constrained Carbenes

Rosenberg

Brinker

2006

Eur J Org Chem

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Carbenes traditionally have been used for cyclopropane synthesis but little else, since their reactions are difficult to control. However, the burgeoning discipline of supramolecular carbene chemistry—reactions in which highly reactive, divalent carbon intermediates are generated within the confines of host compounds—is making steady progress towards solving this problem. Various carbenes generated within cyclodextrins, hemicarcerands, and zeolites demonstrate increased selectivities and lifetimes since their usual decay pathways are blocked. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Absolute rate constants for additions of phenylchlorocarbene to alkenes

Cited by 62 publications

References 0 publications

Divalent Carbon Intermediates: Laser Photolysis and Spectroscopy

Divalent Carbon Intermediates: Laser Photolysis and Spectroscopy

A Half‐Century Odyssey in the Realm of Reactive Intermediates

Constrained Carbenes

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