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 *)]

William Clegg; Neil Feeder; Ana M. Martin Castro; Saifun Nahar; Paul R. Raithby; Gregory P. Shields; Simon J. Teat

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

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 ^*)]

William Clegg, Neil Feeder, Ana M. Martin Castro, Saifun Nahar, Paul R. Raithby, Gregory P. Shields, Simon J. Teat

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

13 Citations (SciVal)

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.

Original language	English
Pages (from-to)	237-246
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	573
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(98)00834-1
Publication status	Published - 31 Jan 1999

Funding

We thank the EPSRC for financial support for the purchase of instrumentation and for fellowships (to N.F. and S.J.T) and for a studentship (to G.P.S). We gratefully acknowledge the financial support of the Cambridge Commonwealth Trust and the United Kingdom Committee of Vice Chancellors and Principals (to S.N.), the Cambridge crystallographic data centre (to G.P.S.), and the CCLRC (to W.C.). A.M.M.C. wishes to thank the Spanish Ministry of Education and the British Council for a grant and for study leave. We are grateful to Johnson Matthey for a generous loan of osmium and rhodium salts.

Keywords

Cluster
Crystal structures
Cyclopentadienyl
Osmium
Rhodium

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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Clegg, W., Feeder, N., Martin Castro, A. M., Nahar, S., Raithby, P. R., Shields, G. P., & Teat, S. J. (1999). 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 ^*)]. Journal of Organometallic Chemistry, 573(1-2), 237-246. https://doi.org/10.1016/S0022-328X(98)00834-1

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 ^*)]. / Clegg, William; Feeder, Neil; Martin Castro, Ana M. et al.
In: Journal of Organometallic Chemistry, Vol. 573, No. 1-2, 31.01.1999, p. 237-246.

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

Clegg, W, Feeder, N, Martin Castro, AM, Nahar, S, Raithby, PR, Shields, GP & Teat, SJ 1999, '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 ^*)]', Journal of Organometallic Chemistry, vol. 573, no. 1-2, pp. 237-246. https://doi.org/10.1016/S0022-328X(98)00834-1

Clegg W, Feeder N, Martin Castro AM, Nahar S, Raithby PR, Shields GP et al. 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 ^*)]. Journal of Organometallic Chemistry. 1999 Jan 31;573(1-2):237-246. doi: 10.1016/S0022-328X(98)00834-1

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title = "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 *)]",

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.",

keywords = "Cluster, Crystal structures, Cyclopentadienyl, Osmium, Rhodium",

author = "William Clegg and Neil Feeder and {Martin Castro}, {Ana M.} and Saifun Nahar and Raithby, {Paul R.} and Shields, {Gregory P.} and Teat, {Simon J.}",

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doi = "10.1016/S0022-328X(98)00834-1",

language = "English",

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T1 - 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 *)]

AU - Clegg, William

AU - Feeder, Neil

AU - Martin Castro, Ana M.

AU - Nahar, Saifun

AU - Raithby, Paul R.

AU - Shields, Gregory P.

AU - Teat, Simon J.

PY - 1999/1/31

Y1 - 1999/1/31

N2 - 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.

AB - 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.

KW - Cluster

KW - Crystal structures

KW - Cyclopentadienyl

KW - Osmium

KW - Rhodium

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