Synthesis and characterisation of novel phosphido- and selenido-substituted ruthenium carbonyl clusters

Brian F.G. Johnson; Teresa M. Layer; Jack Lewis; Paul R. Raithby; Wing Tak Wong

doi:10.1039/DT9930000973

Synthesis and characterisation of novel phosphido- and selenido-substituted ruthenium carbonyl clusters

Brian F.G. Johnson, Teresa M. Layer, Jack Lewis, Paul R. Raithby, Wing Tak Wong

University of Cambridge

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

Abstract

Reaction of the cyclic organophosphorus ligand P₄Bu^t₄ 1 with [Ru₃(CO)₁₂] or [Ru₄H₄(CO)₁₂] under forcing conditions yields a number of novel phosphido- and phosphinidene-substituted ruthenium carbonyl clusters. Three products have been structurally characterised in reasonable yield: [Ru₄(CO)₈(PBu^t)₄] 2, where a square-planar arrangement of four ruthenium atoms is capped above and below the metal-atom plane by two tert-butylphosphinidene ligands, and additionally two μ-phosphinidene ligands bridge two Ru-Ru edges; [Ru₅(CO)₁₅(PBu^t)] 3 in which the five ruthenium atoms adopt a square-pyramidal geometry with the square-basal plane capped by a tert-butylphosphinidene ligand; and [Ru₆H₂(CO)₁₂(PBu^t)₃] 4, where the six ruthenium atoms define an octahedron with triply-bridging phosphinidene groups capping three triangular faces. Clusters 2 and 4 were isolated from the thermolysis of compound 1 with the tetraruthenium substrate [Ru₄H₄(CO)₁₂]; cluster 3 is a product of the thermolysis of 1 with [Ru₃(CO)₁₂]. In addition, the cluster [Ru₄(μ₄-Se)₂-(CO)₈(μ-CO) ₃] 5 has been isolated by the vacuum pyrolysis of [Ru₃(CO)₁₂] with Ph₂Se₂ at 185 °C. Reaction of this cluster with 1,3-bis(diphenylphosphino)propane (dppp) at room temperature affords the triruthenium phosphine-substituted cluster [Ru₃(μ₃-Se)₂(CO)₇(dppp)] 6. The structures of clusters 5 and 6 have also been established by single crystal X-ray analysis.

Original language	English
Pages (from-to)	973-980
Number of pages	8
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	6
DOIs	https://doi.org/10.1039/DT9930000973
Publication status	Published - 1993

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General Chemistry

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@article{9f086788e32a4fd5a93842bab4c4d97a,

title = "Synthesis and characterisation of novel phosphido- and selenido-substituted ruthenium carbonyl clusters",

abstract = "Reaction of the cyclic organophosphorus ligand P4But4 1 with [Ru3(CO)12] or [Ru4H4(CO)12] under forcing conditions yields a number of novel phosphido- and phosphinidene-substituted ruthenium carbonyl clusters. Three products have been structurally characterised in reasonable yield: [Ru4(CO)8(PBut)4] 2, where a square-planar arrangement of four ruthenium atoms is capped above and below the metal-atom plane by two tert-butylphosphinidene ligands, and additionally two μ-phosphinidene ligands bridge two Ru-Ru edges; [Ru5(CO)15(PBut)] 3 in which the five ruthenium atoms adopt a square-pyramidal geometry with the square-basal plane capped by a tert-butylphosphinidene ligand; and [Ru6H2(CO)12(PBut)3] 4, where the six ruthenium atoms define an octahedron with triply-bridging phosphinidene groups capping three triangular faces. Clusters 2 and 4 were isolated from the thermolysis of compound 1 with the tetraruthenium substrate [Ru4H4(CO)12]; cluster 3 is a product of the thermolysis of 1 with [Ru3(CO)12]. In addition, the cluster [Ru4(μ4-Se)2-(CO)8(μ-CO) 3] 5 has been isolated by the vacuum pyrolysis of [Ru3(CO)12] with Ph2Se2 at 185 °C. Reaction of this cluster with 1,3-bis(diphenylphosphino)propane (dppp) at room temperature affords the triruthenium phosphine-substituted cluster [Ru3(μ3-Se)2(CO)7(dppp)] 6. The structures of clusters 5 and 6 have also been established by single crystal X-ray analysis.",

author = "Johnson, {Brian F.G.} and Layer, {Teresa M.} and Jack Lewis and Raithby, {Paul R.} and Wong, {Wing Tak}",

year = "1993",

doi = "10.1039/DT9930000973",

language = "English",

pages = "973--980",

journal = "Journal of the Chemical Society, Dalton Transactions",

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publisher = "Royal Society of Chemistry",

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T1 - Synthesis and characterisation of novel phosphido- and selenido-substituted ruthenium carbonyl clusters

AU - Johnson, Brian F.G.

AU - Layer, Teresa M.

AU - Lewis, Jack

AU - Raithby, Paul R.

AU - Wong, Wing Tak

PY - 1993

Y1 - 1993

N2 - Reaction of the cyclic organophosphorus ligand P4But4 1 with [Ru3(CO)12] or [Ru4H4(CO)12] under forcing conditions yields a number of novel phosphido- and phosphinidene-substituted ruthenium carbonyl clusters. Three products have been structurally characterised in reasonable yield: [Ru4(CO)8(PBut)4] 2, where a square-planar arrangement of four ruthenium atoms is capped above and below the metal-atom plane by two tert-butylphosphinidene ligands, and additionally two μ-phosphinidene ligands bridge two Ru-Ru edges; [Ru5(CO)15(PBut)] 3 in which the five ruthenium atoms adopt a square-pyramidal geometry with the square-basal plane capped by a tert-butylphosphinidene ligand; and [Ru6H2(CO)12(PBut)3] 4, where the six ruthenium atoms define an octahedron with triply-bridging phosphinidene groups capping three triangular faces. Clusters 2 and 4 were isolated from the thermolysis of compound 1 with the tetraruthenium substrate [Ru4H4(CO)12]; cluster 3 is a product of the thermolysis of 1 with [Ru3(CO)12]. In addition, the cluster [Ru4(μ4-Se)2-(CO)8(μ-CO) 3] 5 has been isolated by the vacuum pyrolysis of [Ru3(CO)12] with Ph2Se2 at 185 °C. Reaction of this cluster with 1,3-bis(diphenylphosphino)propane (dppp) at room temperature affords the triruthenium phosphine-substituted cluster [Ru3(μ3-Se)2(CO)7(dppp)] 6. The structures of clusters 5 and 6 have also been established by single crystal X-ray analysis.

AB - Reaction of the cyclic organophosphorus ligand P4But4 1 with [Ru3(CO)12] or [Ru4H4(CO)12] under forcing conditions yields a number of novel phosphido- and phosphinidene-substituted ruthenium carbonyl clusters. Three products have been structurally characterised in reasonable yield: [Ru4(CO)8(PBut)4] 2, where a square-planar arrangement of four ruthenium atoms is capped above and below the metal-atom plane by two tert-butylphosphinidene ligands, and additionally two μ-phosphinidene ligands bridge two Ru-Ru edges; [Ru5(CO)15(PBut)] 3 in which the five ruthenium atoms adopt a square-pyramidal geometry with the square-basal plane capped by a tert-butylphosphinidene ligand; and [Ru6H2(CO)12(PBut)3] 4, where the six ruthenium atoms define an octahedron with triply-bridging phosphinidene groups capping three triangular faces. Clusters 2 and 4 were isolated from the thermolysis of compound 1 with the tetraruthenium substrate [Ru4H4(CO)12]; cluster 3 is a product of the thermolysis of 1 with [Ru3(CO)12]. In addition, the cluster [Ru4(μ4-Se)2-(CO)8(μ-CO) 3] 5 has been isolated by the vacuum pyrolysis of [Ru3(CO)12] with Ph2Se2 at 185 °C. Reaction of this cluster with 1,3-bis(diphenylphosphino)propane (dppp) at room temperature affords the triruthenium phosphine-substituted cluster [Ru3(μ3-Se)2(CO)7(dppp)] 6. The structures of clusters 5 and 6 have also been established by single crystal X-ray analysis.

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ER -

Synthesis and characterisation of novel phosphido- and selenido-substituted ruthenium carbonyl clusters

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