Pyridylhalocarbenes and pyridiniumhalocarbenes

Moss, Robert A.; Jang, Eun G.; Kim, Hong-Rak; Ho, Guo‐Jie; Baird, Mark S.

doi:10.1016/s0040-4039(00)91638-1

Cited by 18 publications

(42 citation statements)

References 13 publications

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“…LFP generation of PyrCCl from diazirine 6 in DCE resulted in the appearance of strong absorption at 468 nm due to the formation of “self-ylide” 9 , stemming from attack of PyrCCl on its precursor diazirine. This reaction is well-known; in isooctane, ylide 9 absorbs at 480 nm. , …”

Section: Resultsmentioning

confidence: 94%

“…As illustrated in Tables 2 and 3, the positively charged pyridinium unit of MePyr + CCl BF 4 − (3) enhances the equilibrium constants for the formation of a carbene−TMB complex (7), or for the addition of chloride to form the pyridinium dichloromethide zwitterion (11); cf. eqs 4 and 8.…”

Section: Discussionmentioning

confidence: 99%

“…( N -Methyl-3-pyridinium)chlorocarbene tetrafluoroborate (MePyr + CCl BF 4 – , 3 ) is a very strongly electrophilic cationic carbene. − The permanent positive charge imposed on the pyridinium substituent should exert significant electrostatic effects on equilibria involving chloride addition (analogous to eq ) or π-complex formation (analogous to eq ). Here, we report experimental and computational studies of these expectations.…”

Section: Introductionmentioning

confidence: 99%

“…Here, we report experimental and computational studies of these expectations. Comparisons are made to equilibria of the uncharged but highly electrophilic carbenes p -trifluoromethylphenylchlorocarbene ( p -F 3 C-PhCCl) and F 5 -PhCCl, , as well as the “parent” carbenes, 4-pyridylchlorocarbene (4-PyrCCl, 4 ) , and phenylchlorocarbene. , …”

Section: Introductionmentioning

confidence: 99%

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Two Equilibria of (N-Methyl-3-pyridinium)chlorocarbene, a Cationic Carbene

2016

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Equilibrium constants and the associated thermodynamic parameters are reported for the equilibria established between the cationic carbene (N-methyl-3-pyridinium)chlorocarbene tetrafluoroborate (MePyr(+)CCl BF4(-), 3) and 1,3,5-trimethoxybenzene (TMB) to form a carbene-TMB complex, as well as between carbene 3 and chloride ion to form the zwitterion, N-methyl-3-pyridinium dichloromethide (10). These equilibrium constants and thermodynamic parameters are contrasted with analogous data for several related carbenes, and the influence of the pyridinium unit in carbene 3 is thereby highlighted. Computational studies augment and elucidate the experimental results.

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Section: Resultsmentioning

confidence: 94%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Two Equilibria of (N-Methyl-3-pyridinium)chlorocarbene, a Cationic Carbene

2016

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“…We examined ( N ‐methyl‐3‐pyridinium)chlorocarbene ( 1 , MePyr + CCl), another very reactive, electrophilic carbene . Computed parameters for MePyr + CCl appear in Table .…”

Section: (N‐methyl‐3‐pyridinium)chlorocarbenementioning

confidence: 99%

Extremely reactive carbenes: electrophiles and nucleophiles

Moss

Wang

Cang

et al. 2016

J of Physical Organic Chem

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aWe describe the intermolecular reactivity toward alkenes of several extremely reactive carbenes as determined by experimental and computational methods. Among the examined species are the electrophiles trifluoromethylchlorocarbene and (N-methyl-3-pyridinium)chlorocarbene and the nucleophiles adamantanylidene and dimethylcarbene. Phenomena discussed include negative activation energies for addition reactions and apparent compensation between the enthalpies and entropies of activation.

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