Synthesis and characterisation of some hexanuclear heterometallic clusters containing arene ligands; the crystal and molecular structures of RuOs5(CO)15(η6-C6H6) and RhOs5(CO)15(η5-C5Me5)

Richard K. Henderson; Patricia A. Jackson; Brian F. G. Johnson; Jack Lewis; Paul R. Raithby

doi:10.1016/S0020-1693(00)92381-8

Synthesis and characterisation of some hexanuclear heterometallic clusters containing arene ligands; the crystal and molecular structures of RuOs₅(CO)₁₅(η⁶-C₆H₆) and RhOs₅(CO)₁₅(η⁵-C₅Me₅)

Richard K. Henderson, Patricia A. Jackson, Brian F. G. Johnson, Jack Lewis, Paul R. Raithby

University of Cambridge

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

Abstract

Treatment of the pentaosmium dianionic cluster [Os₅(CO)₁₅]^2- (1) with either one equivalent of the dication [Ru(η⁶-C₆H₆)(MeCN)₃]²⁺ (2), or one equivalent of [Rh(η⁵-C₅H₅)(MeCN)₃]²⁺ (3), in dichloromethane, at O °C, affords two isomeric forms of the cluster RuOs₅(CO)₁₅(η⁶-C₆H₆) (4), or three isomeric forms of RhOs₅(CO)₁₅(η⁵-C₅Me₅) (5), respectively. One isomeric form of each cluster (4a and 5a) has been characterised crystallographically. The structures of 4a and 5a both contain a bicapped tetrahedral metal core in which the heteroatom occupies one of the two capping positions; this is in accord with the geometry predicted for a six metal atom cluster with 84 valence electrons. Reduction of the cluster 4 with K/Ph₂CO, in tetrahydrofuran, affords the octahedral dianionic cluster [RuOs₅(CO)₁₄(η⁶-C₆H₆)]^2- (6). When this dianion is treated with HBF₄·Et₂O decomposition occurs, and small amounts of the parent cluster 4 are regenerated. Treatment of 6 with [AuPEt₃]Cl/Tl[BF₄] gives the neutral cluster RuOs₅(CO)₁₄(η⁶-C₆H₆)(AuPEt₃)₂ (7).

Original language	English
Pages (from-to)	393-400
Number of pages	8
Journal	Inorganica Chimica Acta
Volume	198-200
DOIs	https://doi.org/10.1016/S0020-1693(00)92381-8
Publication status	Published - 31 Oct 1992

Funding

We gratefully acknowledge the financial support of Christ’s College, Cambridge (P.A.J.).

Funders	Funder number
Christ’s College, Cambridge

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0020-1693(00)92381-8

Cite this

Synthesis and characterisation of some hexanuclear heterometallic clusters containing arene ligands; the crystal and molecular structures of RuOs₅(CO)₁₅(η⁶-C₆H₆) and RhOs₅(CO)₁₅(η⁵-C₅Me₅). / Henderson, Richard K.; Jackson, Patricia A.; Johnson, Brian F. G. et al.
In: Inorganica Chimica Acta, Vol. 198-200, 31.10.1992, p. 393-400.

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

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title = "Synthesis and characterisation of some hexanuclear heterometallic clusters containing arene ligands; the crystal and molecular structures of RuOs5(CO)15(η6-C6H6) and RhOs5(CO)15(η5-C5Me5)",

abstract = "Treatment of the pentaosmium dianionic cluster [Os5(CO)15]2- (1) with either one equivalent of the dication [Ru(η6-C6H6)(MeCN)3]2+ (2), or one equivalent of [Rh(η5-C5H5)(MeCN)3]2+ (3), in dichloromethane, at O °C, affords two isomeric forms of the cluster RuOs5(CO)15(η6-C6H6) (4), or three isomeric forms of RhOs5(CO)15(η5-C5Me5) (5), respectively. One isomeric form of each cluster (4a and 5a) has been characterised crystallographically. The structures of 4a and 5a both contain a bicapped tetrahedral metal core in which the heteroatom occupies one of the two capping positions; this is in accord with the geometry predicted for a six metal atom cluster with 84 valence electrons. Reduction of the cluster 4 with K/Ph2CO, in tetrahydrofuran, affords the octahedral dianionic cluster [RuOs5(CO)14(η6-C6H6)]2- (6). When this dianion is treated with HBF4·Et2O decomposition occurs, and small amounts of the parent cluster 4 are regenerated. Treatment of 6 with [AuPEt3]Cl/Tl[BF4] gives the neutral cluster RuOs5(CO)14(η6-C6H6)(AuPEt3)2 (7).",

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AU - Henderson, Richard K.

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AU - Raithby, Paul R.

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N2 - Treatment of the pentaosmium dianionic cluster [Os5(CO)15]2- (1) with either one equivalent of the dication [Ru(η6-C6H6)(MeCN)3]2+ (2), or one equivalent of [Rh(η5-C5H5)(MeCN)3]2+ (3), in dichloromethane, at O °C, affords two isomeric forms of the cluster RuOs5(CO)15(η6-C6H6) (4), or three isomeric forms of RhOs5(CO)15(η5-C5Me5) (5), respectively. One isomeric form of each cluster (4a and 5a) has been characterised crystallographically. The structures of 4a and 5a both contain a bicapped tetrahedral metal core in which the heteroatom occupies one of the two capping positions; this is in accord with the geometry predicted for a six metal atom cluster with 84 valence electrons. Reduction of the cluster 4 with K/Ph2CO, in tetrahydrofuran, affords the octahedral dianionic cluster [RuOs5(CO)14(η6-C6H6)]2- (6). When this dianion is treated with HBF4·Et2O decomposition occurs, and small amounts of the parent cluster 4 are regenerated. Treatment of 6 with [AuPEt3]Cl/Tl[BF4] gives the neutral cluster RuOs5(CO)14(η6-C6H6)(AuPEt3)2 (7).

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