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Issue 8, 2002
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Some reactions of allenylidene-ruthenium cluster carbonyls with alkynes

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Abstract

Reactions of Ru3(μ-H)(μ3-CCCPh2)(μ-OH)(CO)9 (1) with alkynes and 1,3-diynes are described. With HC[triple bond, length as m-dash]CSiMe3, sequential formation of Ru33-CH(SiMe3)CHCC[double bond, length as m-dash]CPh2}(μ-OH)(CO)9 (3) and Ru33-Me3SiCCHCHC(SiMe3)CC[double bond, length as m-dash]CPh2}(CO)8 (4) occurred, whereas with HC[triple bond, length as m-dash]CPh, the two isomeric complexes Ru33-CRCR′CR′CRCC[double bond, length as m-dash]CPh2)(CO)8 [R = Ph, H, (5a), R′ = H, Ph (5b)] were isolated. These are formed by insertion of the alkyne into an Ru–C bond, with migration of the cluster H atom to the organic ligand. For 5, elimination of the OH group with one alkyne H atom gives water. The metallabenzene complex Ru33-(FcCCH)2CC[double bond, length as m-dash]CPh2}(CO)9 (6) was obtained from 1 and HC[triple bond, length as m-dash]CFc. The allenyl cluster Ru33-Ph2CCC(CPh[double bond, length as m-dash]CHPh)}(μ-OH)(CO)9 (7) is formed from 1 and PhC[triple bond, length as m-dash]CPh. The allenyl complex Ru33-Me3SiCC(C[triple bond, length as m-dash]CSiMe3)CC[double bond, length as m-dash]CPh2}(μ-OH)(CO)9 (8), formed from 1 and Me3SiC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CSiMe3, and with a structure analogous to that of 3, undergoes isomerisation on heating to yield Ru33-Ph2CCCC(C[triple bond, length as m-dash]CSiMe3)[double bond, length as m-dash]CHSiMe3}(μ-OH)(CO)9 (9) by slippage of the organic ligand over the cluster. The reaction between 1 and FcC[triple bond, length as m-dash]CC[triple bond, length as m-dash]CFc affords Ru33-Ph2CCCC(C[triple bond, length as m-dash]CFc)[double bond, length as m-dash]CHFc}(μ-OH)(CO)9 (10), with a structure analogous to that of 9.

Graphical abstract: Some reactions of allenylidene-ruthenium cluster carbonyls with alkynes

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Article information


Submitted
04 Dec 2001
Accepted
12 Feb 2002
First published
25 Mar 2002

J. Chem. Soc., Dalton Trans., 2002, 1678-1686
Article type
Paper

Some reactions of allenylidene-ruthenium cluster carbonyls with alkynes

M. I. Bruce, N. N. Zaitseva, B. W. Skelton and A. H. White, J. Chem. Soc., Dalton Trans., 2002, 1678
DOI: 10.1039/B111088H

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