Mixed-metal cluster chemistry: Part 20. Syntheses, crystal structures and electrochemical studies of W2Ir2(μ-L)(CO)8(η5-C5H4Me)2 (L = dppe, dppf)

Jonathan P. Blitz; Nigel T. Lucas; Mark G. Humphrey

doi:10.1016/S0022-328X(02)01201-9

Mixed-metal cluster chemistry: Part 20. Syntheses, crystal structures and electrochemical studies of W₂Ir₂(μ-L)(CO)₈(η⁵-C₅H₄Me)₂ (L = dppe, dppf)

Jonathan P. Blitz, Nigel T. Lucas, Mark G. Humphrey^*

^*Corresponding author for this work

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

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Abstract

The 60-electron tetrahedral clusters W₂Ir₂(μ-L)(CO)₈(η⁵-C₅H₄Me)₂ [L = dppe (2), dppf (3)] have been prepared from reaction between W₂Ir₂ (CO)₁₀(η⁵-C₅H₄Me)₂ (1) and the corresponding diphosphine in 52 amd 66% yields, respectively. A structiral study of 2 reveals that three edges of a WIr₂ face are spanned by bridging carbonyls, that the irridium-ligated diphosphine coordinates diaxially and that the tungsten-bound methylcyclopentadienyls coordinate axially and apically eith respect to the plane of bridging carbonyls. A structural study of 3 reveals that the dppf ligand bridges an Ir-Ir bond which is also spanned by a bridging carbonyl: tungsten-ligated methylcyclopentadienyl ligands and terminal carbomyls result in electonic asymmetry (17e and 19e irreversible two-electron reduction: the dppf-containing cluster 3 has a further, irrevesible, one-electron oxidation process. UV vis-NIR spectroelectochemical studies of the 2→2⁺→2²⁺ progression reveal the appearance of a low-energy transition on exidation to 2⁺ which perists on further oxidation to 2²⁺.

Original language	English
Pages (from-to)	133-140
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	650
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(02)01201-9
Publication status	Published - 1 May 2002

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title = "Mixed-metal cluster chemistry: Part 20. Syntheses, crystal structures and electrochemical studies of W2Ir2(μ-L)(CO)8(η5-C5H4Me)2 (L = dppe, dppf)",

abstract = "The 60-electron tetrahedral clusters W2Ir2(μ-L)(CO)8(η5-C5H4Me)2 [L = dppe (2), dppf (3)] have been prepared from reaction between W2Ir2 (CO)10(η5-C5H4Me)2 (1) and the corresponding diphosphine in 52 amd 66% yields, respectively. A structiral study of 2 reveals that three edges of a WIr2 face are spanned by bridging carbonyls, that the irridium-ligated diphosphine coordinates diaxially and that the tungsten-bound methylcyclopentadienyls coordinate axially and apically eith respect to the plane of bridging carbonyls. A structural study of 3 reveals that the dppf ligand bridges an Ir-Ir bond which is also spanned by a bridging carbonyl: tungsten-ligated methylcyclopentadienyl ligands and terminal carbomyls result in electonic asymmetry (17e and 19e irreversible two-electron reduction: the dppf-containing cluster 3 has a further, irrevesible, one-electron oxidation process. UV vis-NIR spectroelectochemical studies of the 2→2+→22+ progression reveal the appearance of a low-energy transition on exidation to 2+ which perists on further oxidation to 22+.",

keywords = "Carbonyl, Cluster, Cyclopentadienyl, Iridium, Phosphine, Tungsten",

author = "Blitz, {Jonathan P.} and Lucas, {Nigel T.} and Humphrey, {Mark G.}",

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AU - Blitz, Jonathan P.

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AU - Humphrey, Mark G.

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N2 - The 60-electron tetrahedral clusters W2Ir2(μ-L)(CO)8(η5-C5H4Me)2 [L = dppe (2), dppf (3)] have been prepared from reaction between W2Ir2 (CO)10(η5-C5H4Me)2 (1) and the corresponding diphosphine in 52 amd 66% yields, respectively. A structiral study of 2 reveals that three edges of a WIr2 face are spanned by bridging carbonyls, that the irridium-ligated diphosphine coordinates diaxially and that the tungsten-bound methylcyclopentadienyls coordinate axially and apically eith respect to the plane of bridging carbonyls. A structural study of 3 reveals that the dppf ligand bridges an Ir-Ir bond which is also spanned by a bridging carbonyl: tungsten-ligated methylcyclopentadienyl ligands and terminal carbomyls result in electonic asymmetry (17e and 19e irreversible two-electron reduction: the dppf-containing cluster 3 has a further, irrevesible, one-electron oxidation process. UV vis-NIR spectroelectochemical studies of the 2→2+→22+ progression reveal the appearance of a low-energy transition on exidation to 2+ which perists on further oxidation to 22+.

AB - The 60-electron tetrahedral clusters W2Ir2(μ-L)(CO)8(η5-C5H4Me)2 [L = dppe (2), dppf (3)] have been prepared from reaction between W2Ir2 (CO)10(η5-C5H4Me)2 (1) and the corresponding diphosphine in 52 amd 66% yields, respectively. A structiral study of 2 reveals that three edges of a WIr2 face are spanned by bridging carbonyls, that the irridium-ligated diphosphine coordinates diaxially and that the tungsten-bound methylcyclopentadienyls coordinate axially and apically eith respect to the plane of bridging carbonyls. A structural study of 3 reveals that the dppf ligand bridges an Ir-Ir bond which is also spanned by a bridging carbonyl: tungsten-ligated methylcyclopentadienyl ligands and terminal carbomyls result in electonic asymmetry (17e and 19e irreversible two-electron reduction: the dppf-containing cluster 3 has a further, irrevesible, one-electron oxidation process. UV vis-NIR spectroelectochemical studies of the 2→2+→22+ progression reveal the appearance of a low-energy transition on exidation to 2+ which perists on further oxidation to 22+.

KW - Carbonyl

KW - Cluster

KW - Cyclopentadienyl

KW - Iridium

KW - Phosphine

KW - Tungsten

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Mixed-metal cluster chemistry: Part 20. Syntheses, crystal structures and electrochemical studies of W₂Ir₂(μ-L)(CO)₈(η⁵-C₅H₄Me)₂ (L = dppe, dppf)

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