Redistribution of trialkyl silanes catalyzed by iridium silyl complexes

Sehoon Park; Bong Gon Kim; Inigo Göttker-Schnetmann; Maurice Brookhart

doi:10.1021/cs200629t

Redistribution of trialkyl silanes catalyzed by iridium silyl complexes

Sehoon Park, Bong Gon Kim, Inigo Göttker-Schnetmann, Maurice Brookhart^*

^*Corresponding author for this work

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

35 Scopus citations

Abstract

[Ir(COE) ₂Cl] ₂ reacts with Et ₃SiH at 23 °C to form a binuclear iridium complex (Et ₃Si) ₂(H) ₂Ir(μ-Cl) ₂Ir(H) ₂(SiEt ₃) ₂, 1. Complex 1 reacts further with Et ₃SiH at 60 °C to form a second binuclear iridium complex, Et ₃Si(H) ₂Ir(μ-SiEt ₂) ₂Ir(H) ₂SiEt ₃, 2, containing bridging Et ₂Si groups. Activation of 2 with H ₂ produces trace quantities of a very highly reactive but unobservable species which rapidly and efficiently catalyzes alkyl redistribution reactions of silanes, RR'R''SiH. D ₂ and silane exchange experiments establish reactivity features of both 2 and the reactive intermediate. The intermediate cannot be observed, but it is likely a monomeric iridium silyl silylene complex that catalyzes alkyl scrambling via silane exchanges coupled with 1,3-alkyl migrations between silicon centers. DFT calculations support such a mechanism.

Original language	English
Pages (from-to)	307-316
Number of pages	10
Journal	ACS Catalysis
Volume	2
Issue number	2
DOIs	https://doi.org/10.1021/cs200629t
State	Published - 3 Feb 2012
Externally published	Yes

Keywords

1,3-alkyl migration
H -triggered catalysis
bridged silylene complexes
iridium
low-T NMR spectroscopy
redistribution of silanes

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title = "Redistribution of trialkyl silanes catalyzed by iridium silyl complexes",

abstract = "[Ir(COE) 2Cl] 2 reacts with Et 3SiH at 23 °C to form a binuclear iridium complex (Et 3Si) 2(H) 2Ir(μ-Cl) 2Ir(H) 2(SiEt 3) 2, 1. Complex 1 reacts further with Et 3SiH at 60 °C to form a second binuclear iridium complex, Et 3Si(H) 2Ir(μ-SiEt 2) 2Ir(H) 2SiEt 3, 2, containing bridging Et 2Si groups. Activation of 2 with H 2 produces trace quantities of a very highly reactive but unobservable species which rapidly and efficiently catalyzes alkyl redistribution reactions of silanes, RR'R''SiH. D 2 and silane exchange experiments establish reactivity features of both 2 and the reactive intermediate. The intermediate cannot be observed, but it is likely a monomeric iridium silyl silylene complex that catalyzes alkyl scrambling via silane exchanges coupled with 1,3-alkyl migrations between silicon centers. DFT calculations support such a mechanism.",

keywords = "1,3-alkyl migration, H -triggered catalysis, bridged silylene complexes, iridium, low-T NMR spectroscopy, redistribution of silanes",

author = "Sehoon Park and Kim, {Bong Gon} and Inigo G{\"o}ttker-Schnetmann and Maurice Brookhart",

year = "2012",

month = feb,

day = "3",

doi = "10.1021/cs200629t",

language = "英语",

volume = "2",

pages = "307--316",

journal = "ACS Catalysis",

issn = "2155-5435",

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T1 - Redistribution of trialkyl silanes catalyzed by iridium silyl complexes

AU - Park, Sehoon

AU - Kim, Bong Gon

AU - Göttker-Schnetmann, Inigo

AU - Brookhart, Maurice

PY - 2012/2/3

Y1 - 2012/2/3

N2 - [Ir(COE) 2Cl] 2 reacts with Et 3SiH at 23 °C to form a binuclear iridium complex (Et 3Si) 2(H) 2Ir(μ-Cl) 2Ir(H) 2(SiEt 3) 2, 1. Complex 1 reacts further with Et 3SiH at 60 °C to form a second binuclear iridium complex, Et 3Si(H) 2Ir(μ-SiEt 2) 2Ir(H) 2SiEt 3, 2, containing bridging Et 2Si groups. Activation of 2 with H 2 produces trace quantities of a very highly reactive but unobservable species which rapidly and efficiently catalyzes alkyl redistribution reactions of silanes, RR'R''SiH. D 2 and silane exchange experiments establish reactivity features of both 2 and the reactive intermediate. The intermediate cannot be observed, but it is likely a monomeric iridium silyl silylene complex that catalyzes alkyl scrambling via silane exchanges coupled with 1,3-alkyl migrations between silicon centers. DFT calculations support such a mechanism.

AB - [Ir(COE) 2Cl] 2 reacts with Et 3SiH at 23 °C to form a binuclear iridium complex (Et 3Si) 2(H) 2Ir(μ-Cl) 2Ir(H) 2(SiEt 3) 2, 1. Complex 1 reacts further with Et 3SiH at 60 °C to form a second binuclear iridium complex, Et 3Si(H) 2Ir(μ-SiEt 2) 2Ir(H) 2SiEt 3, 2, containing bridging Et 2Si groups. Activation of 2 with H 2 produces trace quantities of a very highly reactive but unobservable species which rapidly and efficiently catalyzes alkyl redistribution reactions of silanes, RR'R''SiH. D 2 and silane exchange experiments establish reactivity features of both 2 and the reactive intermediate. The intermediate cannot be observed, but it is likely a monomeric iridium silyl silylene complex that catalyzes alkyl scrambling via silane exchanges coupled with 1,3-alkyl migrations between silicon centers. DFT calculations support such a mechanism.

KW - 1,3-alkyl migration

KW - H -triggered catalysis

KW - bridged silylene complexes

KW - iridium

KW - low-T NMR spectroscopy

KW - redistribution of silanes

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U2 - 10.1021/cs200629t

DO - 10.1021/cs200629t

M3 - 文章

AN - SCOPUS:84863033443

SN - 2155-5435

VL - 2

SP - 307

EP - 316

JO - ACS Catalysis

JF - ACS Catalysis

IS - 2

ER -

Redistribution of trialkyl silanes catalyzed by iridium silyl complexes

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Keywords

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