Comparative reactivity of triorganosilanes, HSi(OEt)3 and HSiEt3, with IrCl(CO)(PPh3)2. Formation of IrCl(H)2(CO)(PPh3)2 or Ir(H)2(SiEt3)(CO)(PPh3)2 depending on the substituents at Si

Yasushi Nishihara; Miwa Takemura; Kohtaro Osakada

doi:10.1016/j.ica.2008.12.033

Comparative reactivity of triorganosilanes, HSi(OEt)₃ and HSiEt₃, with IrCl(CO)(PPh₃)₂. Formation of IrCl(H)₂(CO)(PPh₃)₂ or Ir(H)₂(SiEt₃)(CO)(PPh₃)₂ depending on the substituents at Si

Yasushi Nishihara, Miwa Takemura, Kohtaro Osakada

Research Institute for Interdisciplinary Science

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

Abstract

Reaction of HSi(OEt)₃ with IrCl(CO)(PPh₃)₂ (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)₃}(CO)(PPh₃)₂ (1), which is observed by the ¹H and ³¹P{¹H} NMR spectra of the reaction mixture. The same reaction, but in 20:1 molar ratio at 50 °C for 24 h produces IrCl(H)₂(CO)(PPh₃)₂ (2) rather than the expected product Ir(H)₂{Si(OEt)₃}(CO)(PPh₃)₂ (3) that was previously reported to be formed by this reaction. Accompanying formation of Si(OEt)₄, (EtO)₃SiOSi(OEt)₃, and (EtO)₂HSiOSi(OEt)₃ is observed. On the other hand, trialkylhydrosilane HSiEt₃ reacts with IrCl(CO)(PPh₃)₂ (10:1 molar ratio) at 80 °C for 84 h to give Ir(H)₂(SiEt₃)(CO)(PPh₃)₂ (4) in a high yield, accompanying with a release of ClSiEt₃.

Original language	English
Pages (from-to)	2951-2956
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	362
Issue number	8
DOIs	https://doi.org/10.1016/j.ica.2008.12.033
Publication status	Published - Jun 1 2009

Keywords

Hydrido complex
Hydrosilanes
Iridium
Oxidative addition

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/j.ica.2008.12.033

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Comparative reactivity of triorganosilanes, HSi(OEt)₃ and HSiEt₃, with IrCl(CO)(PPh₃)₂. Formation of IrCl(H)₂(CO)(PPh₃)₂ or Ir(H)₂(SiEt₃)(CO)(PPh₃)₂ depending on the substituents at Si. / Nishihara, Yasushi; Takemura, Miwa; Osakada, Kohtaro.
In: Inorganica Chimica Acta, Vol. 362, No. 8, 01.06.2009, p. 2951-2956.

Research output: Contribution to journal › Article › peer-review

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title = "Comparative reactivity of triorganosilanes, HSi(OEt)3 and HSiEt3, with IrCl(CO)(PPh3)2. Formation of IrCl(H)2(CO)(PPh3)2 or Ir(H)2(SiEt3)(CO)(PPh3)2 depending on the substituents at Si",

abstract = "Reaction of HSi(OEt)3 with IrCl(CO)(PPh3)2 (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)3}(CO)(PPh3)2 (1), which is observed by the 1H and 31P{1H} NMR spectra of the reaction mixture. The same reaction, but in 20:1 molar ratio at 50 °C for 24 h produces IrCl(H)2(CO)(PPh3)2 (2) rather than the expected product Ir(H)2{Si(OEt)3}(CO)(PPh3)2 (3) that was previously reported to be formed by this reaction. Accompanying formation of Si(OEt)4, (EtO)3SiOSi(OEt)3, and (EtO)2HSiOSi(OEt)3 is observed. On the other hand, trialkylhydrosilane HSiEt3 reacts with IrCl(CO)(PPh3)2 (10:1 molar ratio) at 80 °C for 84 h to give Ir(H)2(SiEt3)(CO)(PPh3)2 (4) in a high yield, accompanying with a release of ClSiEt3.",

keywords = "Hydrido complex, Hydrosilanes, Iridium, Oxidative addition",

author = "Yasushi Nishihara and Miwa Takemura and Kohtaro Osakada",

note = "Funding Information: This work was partially supported by a Grant-in-aid for Young Scientists No. 13740412 from the Ministry of Education, Culture, Sports, Science and Technology, Japan. ",

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T1 - Comparative reactivity of triorganosilanes, HSi(OEt)3 and HSiEt3, with IrCl(CO)(PPh3)2. Formation of IrCl(H)2(CO)(PPh3)2 or Ir(H)2(SiEt3)(CO)(PPh3)2 depending on the substituents at Si

AU - Nishihara, Yasushi

AU - Takemura, Miwa

AU - Osakada, Kohtaro

N1 - Funding Information: This work was partially supported by a Grant-in-aid for Young Scientists No. 13740412 from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

PY - 2009/6/1

Y1 - 2009/6/1

N2 - Reaction of HSi(OEt)3 with IrCl(CO)(PPh3)2 (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)3}(CO)(PPh3)2 (1), which is observed by the 1H and 31P{1H} NMR spectra of the reaction mixture. The same reaction, but in 20:1 molar ratio at 50 °C for 24 h produces IrCl(H)2(CO)(PPh3)2 (2) rather than the expected product Ir(H)2{Si(OEt)3}(CO)(PPh3)2 (3) that was previously reported to be formed by this reaction. Accompanying formation of Si(OEt)4, (EtO)3SiOSi(OEt)3, and (EtO)2HSiOSi(OEt)3 is observed. On the other hand, trialkylhydrosilane HSiEt3 reacts with IrCl(CO)(PPh3)2 (10:1 molar ratio) at 80 °C for 84 h to give Ir(H)2(SiEt3)(CO)(PPh3)2 (4) in a high yield, accompanying with a release of ClSiEt3.

AB - Reaction of HSi(OEt)3 with IrCl(CO)(PPh3)2 (5:1 molar ratio) at room temperature for 1 h gives IrCl(H){Si(OEt)3}(CO)(PPh3)2 (1), which is observed by the 1H and 31P{1H} NMR spectra of the reaction mixture. The same reaction, but in 20:1 molar ratio at 50 °C for 24 h produces IrCl(H)2(CO)(PPh3)2 (2) rather than the expected product Ir(H)2{Si(OEt)3}(CO)(PPh3)2 (3) that was previously reported to be formed by this reaction. Accompanying formation of Si(OEt)4, (EtO)3SiOSi(OEt)3, and (EtO)2HSiOSi(OEt)3 is observed. On the other hand, trialkylhydrosilane HSiEt3 reacts with IrCl(CO)(PPh3)2 (10:1 molar ratio) at 80 °C for 84 h to give Ir(H)2(SiEt3)(CO)(PPh3)2 (4) in a high yield, accompanying with a release of ClSiEt3.

KW - Hydrido complex

KW - Hydrosilanes

KW - Iridium

KW - Oxidative addition

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