A tungsten silyl alkylidyne complex and its bis(alkylidene) tautomer. Their interconversion and an unusual silyl migration in their reaction with dioxygen

Tianniu Chen, Xin Hao Zhang, Changsheng Wang, Shujian Chen, Zhongzhi Wu, Liting Li, Karn R. Sorasaenee, Jonathan B. Diminnie, Hongjun Pan, Ilia A. Guzei, Arnold L. Rheingold, Yun Dong Wu, Zi Ling Xue

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Abstract

Bis(alkylidene) complex W(=CH-t-Bu) 2(CH 2-t-Bu)(Si-t- BuPh 2) (1a) has been found to be in equilibrium with its alkyl alkylidyne tautomer W(=C-t-Bu)(CH 2-t-Bu) 2(Si-t-BuPh 2) (1b). Bis(alkylidene) complexes are believed to be intermediates in α-H transfer in alkylidyne complexes W(=CSiMe 3)(CH 2-t-Bu) 3 and W(= 13C-t-Bu)(CH 2-t-Bu) 3. The current study represents a rare observation of an exchange between a bis(alkylidene) and an alkyl alkylidyne complex. Thermodynamics and kinetics of the exchange 1a ⇄ 1b have been studied. The equilibrium constant K eq, for the exchange 1a ⇄ 1b is 3.34(0.05) at 287(1) K, and the thermodynamic parameters of the equilibrium measured are △H° = -3.8(0.8) kJ/mol, △S° = -3(3) J/mol-K, and △G° 287K = -3(2) kJ/mol. The rate constants k 1 and k -1 were obtained from 2D exchange spectroscopy between 267 and 297 K and are 0.34(0.03) and 0.10(0.01) s -1, respectively, at 287 K For the conversion 1a - 1b, activation enthalpy and entropy are △H‡ 1 = 75(5) kJ/mol, △S‡ 1 = 8(25) J/mol-K; for the conversion 1b - 1a, △H‡ -1 = 78(5) kJ/ mol, △S‡ -1 = 8(25) J/mol-K. In the reaction of 1 with O 2, the silyl ligand in 1b was found to undergo an unprecedented migration to the alkylidyne ligand to give the alkylidene oxo complex W(=O)[=C(t-Bu)(Si-t-BuPh 2)](CH 2-t-Bu) 2 (2). The structure of 2 has been determined. Density functional theory calculations have been conducted for a series of model 1,2-migration reactions. The results suggest that the formation of 2 might be initiated by a 1,2-silyl migration to generate a triplet W-alkylidene intermediate, which is then trapped by O 2.

Original languageEnglish (US)
Pages (from-to)1214-1224
Number of pages11
JournalOrganometallics
Volume24
Issue number6
DOIs
StatePublished - Mar 14 2005

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alkylidene
Tungsten
tautomers
tungsten
Thermodynamics
methylidyne
Oxygen
Ligands
Equilibrium constants
Density functional theory
Enthalpy
Rate constants
Entropy
Chemical activation
Spectroscopy
Kinetics
thermodynamics
ligands
enthalpy
activation

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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A tungsten silyl alkylidyne complex and its bis(alkylidene) tautomer. Their interconversion and an unusual silyl migration in their reaction with dioxygen. / Chen, Tianniu; Zhang, Xin Hao; Wang, Changsheng; Chen, Shujian; Wu, Zhongzhi; Li, Liting; Sorasaenee, Karn R.; Diminnie, Jonathan B.; Pan, Hongjun; Guzei, Ilia A.; Rheingold, Arnold L.; Wu, Yun Dong; Xue, Zi Ling.

In: Organometallics, Vol. 24, No. 6, 14.03.2005, p. 1214-1224.

Research output: Contribution to journalArticle

Chen, T, Zhang, XH, Wang, C, Chen, S, Wu, Z, Li, L, Sorasaenee, KR, Diminnie, JB, Pan, H, Guzei, IA, Rheingold, AL, Wu, YD & Xue, ZL 2005, 'A tungsten silyl alkylidyne complex and its bis(alkylidene) tautomer. Their interconversion and an unusual silyl migration in their reaction with dioxygen', Organometallics, vol. 24, no. 6, pp. 1214-1224. https://doi.org/10.1021/om049031j
Chen, Tianniu ; Zhang, Xin Hao ; Wang, Changsheng ; Chen, Shujian ; Wu, Zhongzhi ; Li, Liting ; Sorasaenee, Karn R. ; Diminnie, Jonathan B. ; Pan, Hongjun ; Guzei, Ilia A. ; Rheingold, Arnold L. ; Wu, Yun Dong ; Xue, Zi Ling. / A tungsten silyl alkylidyne complex and its bis(alkylidene) tautomer. Their interconversion and an unusual silyl migration in their reaction with dioxygen. In: Organometallics. 2005 ; Vol. 24, No. 6. pp. 1214-1224.
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title = "A tungsten silyl alkylidyne complex and its bis(alkylidene) tautomer. Their interconversion and an unusual silyl migration in their reaction with dioxygen",
abstract = "Bis(alkylidene) complex W(=CH-t-Bu) 2(CH 2-t-Bu)(Si-t- BuPh 2) (1a) has been found to be in equilibrium with its alkyl alkylidyne tautomer W(=C-t-Bu)(CH 2-t-Bu) 2(Si-t-BuPh 2) (1b). Bis(alkylidene) complexes are believed to be intermediates in α-H transfer in alkylidyne complexes W(=CSiMe 3)(CH 2-t-Bu) 3 and W(= 13C-t-Bu)(CH 2-t-Bu) 3. The current study represents a rare observation of an exchange between a bis(alkylidene) and an alkyl alkylidyne complex. Thermodynamics and kinetics of the exchange 1a ⇄ 1b have been studied. The equilibrium constant K eq, for the exchange 1a ⇄ 1b is 3.34(0.05) at 287(1) K, and the thermodynamic parameters of the equilibrium measured are △H° = -3.8(0.8) kJ/mol, △S° = -3(3) J/mol-K, and △G° 287K = -3(2) kJ/mol. The rate constants k 1 and k -1 were obtained from 2D exchange spectroscopy between 267 and 297 K and are 0.34(0.03) and 0.10(0.01) s -1, respectively, at 287 K For the conversion 1a - 1b, activation enthalpy and entropy are △H‡ 1 = 75(5) kJ/mol, △S‡ 1 = 8(25) J/mol-K; for the conversion 1b - 1a, △H‡ -1 = 78(5) kJ/ mol, △S‡ -1 = 8(25) J/mol-K. In the reaction of 1 with O 2, the silyl ligand in 1b was found to undergo an unprecedented migration to the alkylidyne ligand to give the alkylidene oxo complex W(=O)[=C(t-Bu)(Si-t-BuPh 2)](CH 2-t-Bu) 2 (2). The structure of 2 has been determined. Density functional theory calculations have been conducted for a series of model 1,2-migration reactions. The results suggest that the formation of 2 might be initiated by a 1,2-silyl migration to generate a triplet W-alkylidene intermediate, which is then trapped by O 2.",
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TY - JOUR

T1 - A tungsten silyl alkylidyne complex and its bis(alkylidene) tautomer. Their interconversion and an unusual silyl migration in their reaction with dioxygen

AU - Chen, Tianniu

AU - Zhang, Xin Hao

AU - Wang, Changsheng

AU - Chen, Shujian

AU - Wu, Zhongzhi

AU - Li, Liting

AU - Sorasaenee, Karn R.

AU - Diminnie, Jonathan B.

AU - Pan, Hongjun

AU - Guzei, Ilia A.

AU - Rheingold, Arnold L.

AU - Wu, Yun Dong

AU - Xue, Zi Ling

PY - 2005/3/14

Y1 - 2005/3/14

N2 - Bis(alkylidene) complex W(=CH-t-Bu) 2(CH 2-t-Bu)(Si-t- BuPh 2) (1a) has been found to be in equilibrium with its alkyl alkylidyne tautomer W(=C-t-Bu)(CH 2-t-Bu) 2(Si-t-BuPh 2) (1b). Bis(alkylidene) complexes are believed to be intermediates in α-H transfer in alkylidyne complexes W(=CSiMe 3)(CH 2-t-Bu) 3 and W(= 13C-t-Bu)(CH 2-t-Bu) 3. The current study represents a rare observation of an exchange between a bis(alkylidene) and an alkyl alkylidyne complex. Thermodynamics and kinetics of the exchange 1a ⇄ 1b have been studied. The equilibrium constant K eq, for the exchange 1a ⇄ 1b is 3.34(0.05) at 287(1) K, and the thermodynamic parameters of the equilibrium measured are △H° = -3.8(0.8) kJ/mol, △S° = -3(3) J/mol-K, and △G° 287K = -3(2) kJ/mol. The rate constants k 1 and k -1 were obtained from 2D exchange spectroscopy between 267 and 297 K and are 0.34(0.03) and 0.10(0.01) s -1, respectively, at 287 K For the conversion 1a - 1b, activation enthalpy and entropy are △H‡ 1 = 75(5) kJ/mol, △S‡ 1 = 8(25) J/mol-K; for the conversion 1b - 1a, △H‡ -1 = 78(5) kJ/ mol, △S‡ -1 = 8(25) J/mol-K. In the reaction of 1 with O 2, the silyl ligand in 1b was found to undergo an unprecedented migration to the alkylidyne ligand to give the alkylidene oxo complex W(=O)[=C(t-Bu)(Si-t-BuPh 2)](CH 2-t-Bu) 2 (2). The structure of 2 has been determined. Density functional theory calculations have been conducted for a series of model 1,2-migration reactions. The results suggest that the formation of 2 might be initiated by a 1,2-silyl migration to generate a triplet W-alkylidene intermediate, which is then trapped by O 2.

AB - Bis(alkylidene) complex W(=CH-t-Bu) 2(CH 2-t-Bu)(Si-t- BuPh 2) (1a) has been found to be in equilibrium with its alkyl alkylidyne tautomer W(=C-t-Bu)(CH 2-t-Bu) 2(Si-t-BuPh 2) (1b). Bis(alkylidene) complexes are believed to be intermediates in α-H transfer in alkylidyne complexes W(=CSiMe 3)(CH 2-t-Bu) 3 and W(= 13C-t-Bu)(CH 2-t-Bu) 3. The current study represents a rare observation of an exchange between a bis(alkylidene) and an alkyl alkylidyne complex. Thermodynamics and kinetics of the exchange 1a ⇄ 1b have been studied. The equilibrium constant K eq, for the exchange 1a ⇄ 1b is 3.34(0.05) at 287(1) K, and the thermodynamic parameters of the equilibrium measured are △H° = -3.8(0.8) kJ/mol, △S° = -3(3) J/mol-K, and △G° 287K = -3(2) kJ/mol. The rate constants k 1 and k -1 were obtained from 2D exchange spectroscopy between 267 and 297 K and are 0.34(0.03) and 0.10(0.01) s -1, respectively, at 287 K For the conversion 1a - 1b, activation enthalpy and entropy are △H‡ 1 = 75(5) kJ/mol, △S‡ 1 = 8(25) J/mol-K; for the conversion 1b - 1a, △H‡ -1 = 78(5) kJ/ mol, △S‡ -1 = 8(25) J/mol-K. In the reaction of 1 with O 2, the silyl ligand in 1b was found to undergo an unprecedented migration to the alkylidyne ligand to give the alkylidene oxo complex W(=O)[=C(t-Bu)(Si-t-BuPh 2)](CH 2-t-Bu) 2 (2). The structure of 2 has been determined. Density functional theory calculations have been conducted for a series of model 1,2-migration reactions. The results suggest that the formation of 2 might be initiated by a 1,2-silyl migration to generate a triplet W-alkylidene intermediate, which is then trapped by O 2.

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