On the mechanism of silylformylation catalyzed by Rh-Co mixed metal complexes

Iwao Ojima; Zhaoyang Li; Robert J. Donovan; Patrizia Ingallina

doi:10.1016/s0020-1693(97)05855-6

On the mechanism of silylformylation catalyzed by Rh-Co mixed metal complexes

Iwao Ojima
, Zhaoyang Li
, Robert J. Donovan
, Patrizia Ingallina

Chemistry

Stony Brook University

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

28 Scopus citations

Abstract

Possible mechanisms for the silylformylation of 1-alkynes catalyzed by Rh₂Co₂(CO)₁₂ are investigated. Novel Rh-Co mixed metal complexes, (PhMe₂Si)₂Rh(CO)_nCo(CO)₄ (n = 2 or 3) (3) and RhCo(HC≡CBuⁿ) (CO)₅ (5), are found to play important roles in this catalysis. The reaction of 3 with 1-hexyne and HSiMe₂Ph at ambient temperature and pressure of CO gives n-BuC(CHO)=CHSiMe₂Ph (1a, Z/E = 95/5), (PhMe₂Si)₂Rh(CO)₃Co(CO)₄ (3-B) and an Rh-Co mixed metal butterfly complex, Rh₂Co₂(HC≡CBuⁿ)(CO)₁₀ (4). The reaction of 5 with 1-hexyne and HSiMe₂Ph under the same ambient conditions affords 1a (100% Z) very cleanly as the sole reaction product. The crossover experiments using RhCo(DC≡CBuⁿ) (CO)₅ (5-d), 1-hexyne-1d and DSiMe₂Ph strongly support the mixed metal bimetallic catalysis, and involvement of bis(alkyne)-Rh-Co species. The most plausible catalytic cycle of silylformylation which can accommodate all the observed results is proposed.

Original language	English
Pages (from-to)	279-284
Number of pages	6
Journal	Inorganica Chimica Acta
Volume	270
Issue number	1-2
DOIs	https://doi.org/10.1016/s0020-1693(97)05855-6
State	Published - Apr 2 1998

Keywords

Cobalt complexes
Mixed-metal complexes
Rhodium complexes
Silylformylation

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title = "On the mechanism of silylformylation catalyzed by Rh-Co mixed metal complexes",

abstract = "Possible mechanisms for the silylformylation of 1-alkynes catalyzed by Rh2Co2(CO)12 are investigated. Novel Rh-Co mixed metal complexes, (PhMe2Si)2Rh(CO)nCo(CO)4 (n = 2 or 3) (3) and RhCo(HC≡CBun) (CO)5 (5), are found to play important roles in this catalysis. The reaction of 3 with 1-hexyne and HSiMe2Ph at ambient temperature and pressure of CO gives n-BuC(CHO)=CHSiMe2Ph (1a, Z/E = 95/5), (PhMe2Si)2Rh(CO)3Co(CO)4 (3-B) and an Rh-Co mixed metal butterfly complex, Rh2Co2(HC≡CBun)(CO)10 (4). The reaction of 5 with 1-hexyne and HSiMe2Ph under the same ambient conditions affords 1a (100\% Z) very cleanly as the sole reaction product. The crossover experiments using RhCo(DC≡CBun) (CO)5 (5-d), 1-hexyne-1d and DSiMe2Ph strongly support the mixed metal bimetallic catalysis, and involvement of bis(alkyne)-Rh-Co species. The most plausible catalytic cycle of silylformylation which can accommodate all the observed results is proposed.",

keywords = "Cobalt complexes, Mixed-metal complexes, Rhodium complexes, Silylformylation",

author = "Iwao Ojima and Zhaoyang Li and Donovan, \{Robert J.\} and Patrizia Ingallina",

year = "1998",

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doi = "10.1016/s0020-1693(97)05855-6",

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T1 - On the mechanism of silylformylation catalyzed by Rh-Co mixed metal complexes

AU - Ojima, Iwao

AU - Li, Zhaoyang

AU - Donovan, Robert J.

AU - Ingallina, Patrizia

PY - 1998/4/2

Y1 - 1998/4/2

N2 - Possible mechanisms for the silylformylation of 1-alkynes catalyzed by Rh2Co2(CO)12 are investigated. Novel Rh-Co mixed metal complexes, (PhMe2Si)2Rh(CO)nCo(CO)4 (n = 2 or 3) (3) and RhCo(HC≡CBun) (CO)5 (5), are found to play important roles in this catalysis. The reaction of 3 with 1-hexyne and HSiMe2Ph at ambient temperature and pressure of CO gives n-BuC(CHO)=CHSiMe2Ph (1a, Z/E = 95/5), (PhMe2Si)2Rh(CO)3Co(CO)4 (3-B) and an Rh-Co mixed metal butterfly complex, Rh2Co2(HC≡CBun)(CO)10 (4). The reaction of 5 with 1-hexyne and HSiMe2Ph under the same ambient conditions affords 1a (100% Z) very cleanly as the sole reaction product. The crossover experiments using RhCo(DC≡CBun) (CO)5 (5-d), 1-hexyne-1d and DSiMe2Ph strongly support the mixed metal bimetallic catalysis, and involvement of bis(alkyne)-Rh-Co species. The most plausible catalytic cycle of silylformylation which can accommodate all the observed results is proposed.

AB - Possible mechanisms for the silylformylation of 1-alkynes catalyzed by Rh2Co2(CO)12 are investigated. Novel Rh-Co mixed metal complexes, (PhMe2Si)2Rh(CO)nCo(CO)4 (n = 2 or 3) (3) and RhCo(HC≡CBun) (CO)5 (5), are found to play important roles in this catalysis. The reaction of 3 with 1-hexyne and HSiMe2Ph at ambient temperature and pressure of CO gives n-BuC(CHO)=CHSiMe2Ph (1a, Z/E = 95/5), (PhMe2Si)2Rh(CO)3Co(CO)4 (3-B) and an Rh-Co mixed metal butterfly complex, Rh2Co2(HC≡CBun)(CO)10 (4). The reaction of 5 with 1-hexyne and HSiMe2Ph under the same ambient conditions affords 1a (100% Z) very cleanly as the sole reaction product. The crossover experiments using RhCo(DC≡CBun) (CO)5 (5-d), 1-hexyne-1d and DSiMe2Ph strongly support the mixed metal bimetallic catalysis, and involvement of bis(alkyne)-Rh-Co species. The most plausible catalytic cycle of silylformylation which can accommodate all the observed results is proposed.

KW - Cobalt complexes

KW - Mixed-metal complexes

KW - Rhodium complexes

KW - Silylformylation

UR - https://www.scopus.com/pages/publications/0000344559

U2 - 10.1016/s0020-1693(97)05855-6

DO - 10.1016/s0020-1693(97)05855-6

M3 - Article

AN - SCOPUS:0000344559

SN - 0020-1693

VL - 270

SP - 279

EP - 284

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 1-2

ER -

On the mechanism of silylformylation catalyzed by Rh-Co mixed metal complexes

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