Mixed-metal cluster chemistry. 26 [1]. Proclivity for "all-terminal" or "plane-of-bridging-carbonyls" ligand disposition in tungsten-triiridium clusters

Alistair J. Usher; Gulliver T. Dalton; Nigel T. Lucas; Susan M. Waterman; Simon Petrie; Robert Stranger; Mark G. Humphrey; Anthony C. Willis

doi:10.1016/j.jorganchem.2003.09.026

Mixed-metal cluster chemistry. 26 [1]. Proclivity for "all-terminal" or "plane-of-bridging-carbonyls" ligand disposition in tungsten-triiridium clusters

Alistair J. Usher, Gulliver T. Dalton, Nigel T. Lucas, Susan M. Waterman, Simon Petrie, Robert Stranger, Mark G. Humphrey^*, Anthony C. Willis

^*Corresponding author for this work

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

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Abstract

Reaction of WH(CO)₃(η-C₅Me₅) with IrCl(CO)₂(4-H₂NC₆H₄Me) affords WIr₃(μ-CO)₃(CO)₈ (η-C₅Me₅) in low yield. A structural study reveals a WIr₂-centred plane of bridging carbonyls, in contrast to the crystal structure of WIr₃(CO)₁₁ (η-C₅H₅) (all-terminal carbonyl distribution). DFT calculations reveal an increasing proclivity to adopt an all-terminal CO disposition for clusters MIr₃(CO)₁₁ (η-C₅H₅) in the gas phase on proceeding from M=Cr to Mo and then W, consistent with structural studies in the solid state for which the tungsten-containing cluster is the only all-terminal example. Increasing electron donation from the ligands in the tungsten system (either from phosphine substitution or cyclopentadienyl permethylation) suffices to impose a plane of bridging carbonyls in the ground state structure. ¹³C NMR fluxionality studies reveal that CO exchange mechanism(s) for WIr₃(CO)₁₁ (η-C₅H₅) and the related tetrahedral cluster W₂Ir₂(CO)₁₀(η-C₅ H₅)₂ are very fast and involve all carbonyls on the clusters. DFT calculations on MIr₃(CO)₁₁ (η-C₅H₅) (M=Cr, Mo) substantiate a ' merry-go-round' mechanism for carbonyl scrambling in these systems, a result which is consistent with the scrambling behaviour seen in the NMR fluxionality studies on the W-containing congener.

Original language	English
Pages (from-to)	50-57
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	689
Issue number	1
DOIs	https://doi.org/10.1016/j.jorganchem.2003.09.026
Publication status	Published - 5 Jan 2004

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Usher, A. J., Dalton, G. T., Lucas, N. T., Waterman, S. M., Petrie, S., Stranger, R., Humphrey, M. G., & Willis, A. C. (2004). Mixed-metal cluster chemistry. 26 [1]. Proclivity for "all-terminal" or "plane-of-bridging-carbonyls" ligand disposition in tungsten-triiridium clusters. Journal of Organometallic Chemistry, 689(1), 50-57. https://doi.org/10.1016/j.jorganchem.2003.09.026

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title = "Mixed-metal cluster chemistry. 26 [1]. Proclivity for {"}all-terminal{"} or {"}plane-of-bridging-carbonyls{"} ligand disposition in tungsten-triiridium clusters",

abstract = "Reaction of WH(CO)3(η-C5Me5) with IrCl(CO)2(4-H2NC6H4Me) affords WIr3(μ-CO)3(CO)8 (η-C5Me5) in low yield. A structural study reveals a WIr2-centred plane of bridging carbonyls, in contrast to the crystal structure of WIr3(CO)11 (η-C5H5) (all-terminal carbonyl distribution). DFT calculations reveal an increasing proclivity to adopt an all-terminal CO disposition for clusters MIr3(CO)11 (η-C5H5) in the gas phase on proceeding from M=Cr to Mo and then W, consistent with structural studies in the solid state for which the tungsten-containing cluster is the only all-terminal example. Increasing electron donation from the ligands in the tungsten system (either from phosphine substitution or cyclopentadienyl permethylation) suffices to impose a plane of bridging carbonyls in the ground state structure. 13C NMR fluxionality studies reveal that CO exchange mechanism(s) for WIr3(CO)11 (η-C5H5) and the related tetrahedral cluster W2Ir2(CO)10(η-C5 H5)2 are very fast and involve all carbonyls on the clusters. DFT calculations on MIr3(CO)11 (η-C5H5) (M=Cr, Mo) substantiate a ' merry-go-round' mechanism for carbonyl scrambling in these systems, a result which is consistent with the scrambling behaviour seen in the NMR fluxionality studies on the W-containing congener.",

keywords = "Carbonyl, Chromium, Cluster, Crystal structure, Cyclopentadienyl, Density functional theory, Fluxionality, Iridium, Molybdenum, Tungsten",

author = "Usher, {Alistair J.} and Dalton, {Gulliver T.} and Lucas, {Nigel T.} and Waterman, {Susan M.} and Simon Petrie and Robert Stranger and Humphrey, {Mark G.} and Willis, {Anthony C.}",

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language = "English",

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Usher, AJ, Dalton, GT, Lucas, NT, Waterman, SM, Petrie, S, Stranger, R, Humphrey, MG & Willis, AC 2004, 'Mixed-metal cluster chemistry. 26 [1]. Proclivity for "all-terminal" or "plane-of-bridging-carbonyls" ligand disposition in tungsten-triiridium clusters', Journal of Organometallic Chemistry, vol. 689, no. 1, pp. 50-57. https://doi.org/10.1016/j.jorganchem.2003.09.026

TY - JOUR

T1 - Mixed-metal cluster chemistry. 26 [1]. Proclivity for "all-terminal" or "plane-of-bridging-carbonyls" ligand disposition in tungsten-triiridium clusters

AU - Usher, Alistair J.

AU - Dalton, Gulliver T.

AU - Lucas, Nigel T.

AU - Waterman, Susan M.

AU - Petrie, Simon

AU - Stranger, Robert

AU - Humphrey, Mark G.

AU - Willis, Anthony C.

PY - 2004/1/5

Y1 - 2004/1/5

N2 - Reaction of WH(CO)3(η-C5Me5) with IrCl(CO)2(4-H2NC6H4Me) affords WIr3(μ-CO)3(CO)8 (η-C5Me5) in low yield. A structural study reveals a WIr2-centred plane of bridging carbonyls, in contrast to the crystal structure of WIr3(CO)11 (η-C5H5) (all-terminal carbonyl distribution). DFT calculations reveal an increasing proclivity to adopt an all-terminal CO disposition for clusters MIr3(CO)11 (η-C5H5) in the gas phase on proceeding from M=Cr to Mo and then W, consistent with structural studies in the solid state for which the tungsten-containing cluster is the only all-terminal example. Increasing electron donation from the ligands in the tungsten system (either from phosphine substitution or cyclopentadienyl permethylation) suffices to impose a plane of bridging carbonyls in the ground state structure. 13C NMR fluxionality studies reveal that CO exchange mechanism(s) for WIr3(CO)11 (η-C5H5) and the related tetrahedral cluster W2Ir2(CO)10(η-C5 H5)2 are very fast and involve all carbonyls on the clusters. DFT calculations on MIr3(CO)11 (η-C5H5) (M=Cr, Mo) substantiate a ' merry-go-round' mechanism for carbonyl scrambling in these systems, a result which is consistent with the scrambling behaviour seen in the NMR fluxionality studies on the W-containing congener.

AB - Reaction of WH(CO)3(η-C5Me5) with IrCl(CO)2(4-H2NC6H4Me) affords WIr3(μ-CO)3(CO)8 (η-C5Me5) in low yield. A structural study reveals a WIr2-centred plane of bridging carbonyls, in contrast to the crystal structure of WIr3(CO)11 (η-C5H5) (all-terminal carbonyl distribution). DFT calculations reveal an increasing proclivity to adopt an all-terminal CO disposition for clusters MIr3(CO)11 (η-C5H5) in the gas phase on proceeding from M=Cr to Mo and then W, consistent with structural studies in the solid state for which the tungsten-containing cluster is the only all-terminal example. Increasing electron donation from the ligands in the tungsten system (either from phosphine substitution or cyclopentadienyl permethylation) suffices to impose a plane of bridging carbonyls in the ground state structure. 13C NMR fluxionality studies reveal that CO exchange mechanism(s) for WIr3(CO)11 (η-C5H5) and the related tetrahedral cluster W2Ir2(CO)10(η-C5 H5)2 are very fast and involve all carbonyls on the clusters. DFT calculations on MIr3(CO)11 (η-C5H5) (M=Cr, Mo) substantiate a ' merry-go-round' mechanism for carbonyl scrambling in these systems, a result which is consistent with the scrambling behaviour seen in the NMR fluxionality studies on the W-containing congener.

KW - Carbonyl

KW - Chromium

KW - Cluster

KW - Crystal structure

KW - Cyclopentadienyl

KW - Density functional theory

KW - Fluxionality

KW - Iridium

KW - Molybdenum

KW - Tungsten

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U2 - 10.1016/j.jorganchem.2003.09.026

DO - 10.1016/j.jorganchem.2003.09.026

M3 - Article

SN - 0022-328X

VL - 689

SP - 50

EP - 57

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1

ER -

Mixed-metal cluster chemistry. 26 [1]. Proclivity for "all-terminal" or "plane-of-bridging-carbonyls" ligand disposition in tungsten-triiridium clusters

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