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Molecular rearrangements of diynes coordinated to triosmium carbonyl clusters: the synthesis and structural characterisation of [Os-3(mu-H)(CO)(10){mu(3)-eta(1):eta(3):eta(1)-Ph(C)C9H6)}], [Os-3(mu-H)(CO)(9){mu(3)- eta(1):eta(3):eta(1)-Ph(C)C9H6)}] and [Os-3(mu-H)(CO)(8)(MeCN){mu(3)-eta(1):eta(3):eta(1)- Ph(C)C9H6)}]


Reference:

Clarke, L. P., Davies, J. E., Krupenya, D. V., Raithby, P. R., Shields, G. P., Starova, G. L. and Tunik, S. P., 2003. Molecular rearrangements of diynes coordinated to triosmium carbonyl clusters: the synthesis and structural characterisation of [Os-3(mu-H)(CO)(10){mu(3)-eta(1):eta(3):eta(1)-Ph(C)C9H6)}], [Os-3(mu-H)(CO)(9){mu(3)- eta(1):eta(3):eta(1)-Ph(C)C9H6)}] and [Os-3(mu-H)(CO)(8)(MeCN){mu(3)-eta(1):eta(3):eta(1)- Ph(C)C9H6)}]. Journal of Organometallic Chemistry, 683 (2), pp. 313-323.

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Abstract

The reaction between [Os3H2(CO)(10)] and 1,4-diphenylbuta-1,3-diyne yields two isomers of the triosmium cluster [Os-3(mu-H)(CO)(10){mu(3)-eta(1):eta(3) eta(1)-Ph(C)C9H6)}]1, 2, the structures of which involve an 'open' metal triangle and exhibit an unusual pseudo-allylic interaction involving a fused six- and five-membered ring system obtained from a ring-closure reaction of the diyne. Thermal decarbonylation of 1 and 2 produces [Os-3(mu-H)(CO)(9){mu3-eta(1):eta(3):eta(1)-Ph(C)C9H6)}] (3) which has a 'closed' Os-3 triangular core and the same formal mu(3)-eta(1):eta(3):eta(1)-allylic coordination mode. The reaction of 1 with trimethylamine-N-oxide in the presence of acetonitrile affords [Os-3(mu-H)(CO)(8)(MeCN) {mu(3)-eta(1):eta(3):eta(1)-(Ph(C)C9H6)}] (4), an acetonitrile-substituted derivative of 3. The structures of clusters 1-4 have been established by X-ray crystallography, and all the new clusters have been characterised spectroscopically. (C) 2003 Elsevier B.V. All rights reserved.

Details

Item Type Articles
CreatorsClarke, L. P., Davies, J. E., Krupenya, D. V., Raithby, P. R., Shields, G. P., Starova, G. L. and Tunik, S. P.
DOI10.1016/s0022-328x(03)00537-0
DepartmentsFaculty of Science > Chemistry
RefereedYes
StatusPublished
ID Code5045
Additional InformationID number: ISI:000186295600006

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