1995
DOI: 10.1021/ja00118a004
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A Computational and Experimental Investigation of "Free" tert-Butylmethylene, a Carbene Stabilized by .sigma. Bond Participation

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Cited by 28 publications
(33 citation statements)
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“…The structures of related alkyl carbenes, which can be stabilized by hyperconjugation, [45][46][47] also depend strongly on the inclusion of dynamic correlation. 48 However, 4-C s is lower in energy than 4-C 1 by 0.1 kcal mol -1 after inclusion of ZPVE corrections. The zero-point averaged structure may therefore be effectively of C s symmetry.…”
Section: Resultsmentioning
confidence: 95%
“…The structures of related alkyl carbenes, which can be stabilized by hyperconjugation, [45][46][47] also depend strongly on the inclusion of dynamic correlation. 48 However, 4-C s is lower in energy than 4-C 1 by 0.1 kcal mol -1 after inclusion of ZPVE corrections. The zero-point averaged structure may therefore be effectively of C s symmetry.…”
Section: Resultsmentioning
confidence: 95%
“…An inspection of the minimized geometry calculated for singlet 2a in Figure reveals a Me−C α −C carbene angle of 101.0°, in marked contrast to the angle of 79.8° calculated for carbene 1 . While the smaller than normal Me−C α −C carbene angle in 2 indicates some stabilization by the adjacent C−C σ bond, the effect is far less dramatic than in 1 .…”
Section: Resultsmentioning
confidence: 77%
“…This problem has been circumvented in two general ways. The first is simply to avoid the use of nitrogenous precursors and employ alternatives such as the deoxygenation of carbonyl compounds by atomic carbon ,, and cheleotropic extrusion of carbenes from cyclopropanes. , The second approach is to use a nitrogenous precursor followed by rearrangement to a new carbene that is distinctively separated from its precursor on the reactive energy surface. This method has been used successfully by generating a carbene that undergoes the phenylcarbene rearrangement , to a new carbene that is now capable of intramolecular rearrangement to stable products. , In the present investigation, we have used the second of these approaches to study 2 .…”
Section: Resultsmentioning
confidence: 99%
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“…It is likely that 5 results from an initial insertion into a methyl C−H bond to give carbene 7 followed by a 1,2-hydrogen shift (eq 3). The possibility that 6 results from an intramolecular insertion of 7 into an ortho C−H bond is ruled out by generating 7 by the C atom deoxygenation of aldehyde 8 and observing that 5 is the only product (eq 4) 1
…”
Section: Resultsmentioning
confidence: 99%