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Cluster build-up reactions via the ionic coupling of tetraosmium anions and the [RhCp*(NCMe)3]2+ cation; The crystal and molecular structures of [Os4Rh(μ-H)3(MeC=NH)(CO)11(η 5-Cp*)], [Os4Rh(μ-H)2(CO)13(η5-Cp *)]

Lookup NU author(s): Emeritus Professor Bill CleggORCiD

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Abstract

The reaction of [Os4H4(CO)11]2- 2, formed by the reduction of [Os4H4(CO)12] 1 with K/Ph2CO, with the cation [Rh(η5-Cp*)(MeCN)3]2+ (Cp*=C5Me5) 3, affords a number of penta- and hexanuclear mixed-metal clusters depending on the reaction conditions. If only sufficient K/Ph2CO is added to dissolve all of 1, and the dication 3 added, a low yield of a blue cluster [Os4Rh(μ-H)3(MeC=NH)(CO)11(η 5-Cp*)] (Cp*=C5Me5) 4 is obtained in addition to large quantities of 1. If an excess of K/Ph2CO is added so that reduction of 1 is complete, and then the dication 3 added, two new products [Os4Rh(μ-H)2(CO)13(η 5-Cp*)] 5 and [Os4Rh2(μ-H)2(CO)11(η 5-Cp*)2] 6 are obtained in low yield. The three new complexes have been characterised spectroscopically and crystallographically. Cluster 4 contains the uncommon MeC=NH group coordinated to an edge-bridged tetrahedral metal framework. The metal framework in 5 is also a Rh edge-bridged Os4 tetrahedron while that of 6 is a bicapped tetrahedron, with two Rh atoms face capping two faces of an Os4 tetrahedron.

Publication metadata

Author(s): Clegg W, Feeder N, Martin Castro AM, Nahar S, Raithby PR, Shields GP, Teat SJ

Publication type: Article

Publication status: Published

Journal: Journal of Organometallic Chemistry

Year: 1999

Volume: 573

Issue: 1-2

Pages: 237-246

Print publication date: 31/01/1999

ISSN (print): 0022-328X

ISSN (electronic): 1872-8561

Publisher: Elsevier S.A.

URL: http://dx.doi.org/10.1016/S0022-328X(98)00834-1

DOI: 10.1016/S0022-328X(98)00834-1

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