Syntheses of Ir4(CO)6(η5-C5Me4H)2 and Ir7(μ3-CO)3(CO)12(η5-C5Me5) from pentametallic molybdenum-iridium cluster precursors

Junhong Fu; Michael D. Randles; Alan L. Criddle; Graeme J. Moxey; Torsten Schwich; Robert Stranger; Marie P. Cifuentes; Mark G. Humphrey

doi:10.1002/ejic.201500188

Syntheses of Ir₄(CO)₆(η⁵-C₅Me₄H)₂ and Ir₇(μ₃-CO)₃(CO)₁₂(η⁵-C₅Me₅) from pentametallic molybdenum-iridium cluster precursors

Junhong Fu, Michael D. Randles, Alan L. Criddle, Graeme J. Moxey, Torsten Schwich, Robert Stranger, Marie P. Cifuentes, Mark G. Humphrey^*

^*Corresponding author for this work

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

3 Citations (Scopus)

Abstract

Abstract Reaction of Mo₂Ir₃(μ-CO)₃(CO)₆(η⁵-C₅H₅)₂(η⁵-C₅Me₅) with Ir(CO)₂(η⁵-C₅Me₄H) afforded the four-valence-electron-deficient butterfly cluster Ir₄(CO)₆(η⁵-C₅Me₄H)₂; its stability has been rationalized with the aid of density functional theory calculations, which suggest that significant additional intracluster bonding alleviates the formal electron deficiency. Reaction of MoIr₄(CO)₁₀(η⁵-C₅H₅)(η⁵-C₅Me₅) with [N(PPh₃)₂][Ir(CO)₄] afforded the capped octahedral cluster Ir₇(μ₃-CO)₃(CO)₁₂(η⁵-C₅Me₅), which possesses three semi-face-capping CO ligands. These outcomes demonstrate that heterometallic clusters may serve as a potential source of new homometallic clusters following appropriate M-M′ cleavage. Reactions of molybdenum-iridium clusters with iridium-containing reagents afforded new homometallic clusters. Ir₇(μ₃-CO)₃(CO)₁₂(η⁵-C₅Me₅) possesses three semi-face-capping CO ligands, while Ir₄(CO)₆(η⁵-C₅Me₄H) is formally very electron-deficient; theoretical studies suggest stabilization by significant intracluster multiple Ir-Ir bonding.

Original language	English
Pages (from-to)	2587-2591
Number of pages	5
Journal	European Journal of Inorganic Chemistry
Volume	2015
Issue number	15
DOIs	https://doi.org/10.1002/ejic.201500188
Publication status	Published - 1 May 2015

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@article{ba82d7d07301404bbdb1c7be640969c9,

title = "Syntheses of Ir4(CO)6(η5-C5Me4H)2 and Ir7(μ3-CO)3(CO)12(η5-C5Me5) from pentametallic molybdenum-iridium cluster precursors",

abstract = "Abstract Reaction of Mo2Ir3(μ-CO)3(CO)6(η5-C5H5)2(η5-C5Me5) with Ir(CO)2(η5-C5Me4H) afforded the four-valence-electron-deficient butterfly cluster Ir4(CO)6(η5-C5Me4H)2; its stability has been rationalized with the aid of density functional theory calculations, which suggest that significant additional intracluster bonding alleviates the formal electron deficiency. Reaction of MoIr4(CO)10(η5-C5H5)(η5-C5Me5) with [N(PPh3)2][Ir(CO)4] afforded the capped octahedral cluster Ir7(μ3-CO)3(CO)12(η5-C5Me5), which possesses three semi-face-capping CO ligands. These outcomes demonstrate that heterometallic clusters may serve as a potential source of new homometallic clusters following appropriate M-M′ cleavage. Reactions of molybdenum-iridium clusters with iridium-containing reagents afforded new homometallic clusters. Ir7(μ3-CO)3(CO)12(η5-C5Me5) possesses three semi-face-capping CO ligands, while Ir4(CO)6(η5-C5Me4H) is formally very electron-deficient; theoretical studies suggest stabilization by significant intracluster multiple Ir-Ir bonding.",

keywords = "Cluster compounds, Electron-deficient compounds, Solid-state structures, Synthesis design, Transition metals",

author = "Junhong Fu and Randles, {Michael D.} and Criddle, {Alan L.} and Moxey, {Graeme J.} and Torsten Schwich and Robert Stranger and Cifuentes, {Marie P.} and Humphrey, {Mark G.}",

note = "Publisher Copyright: Copyright {\textcopyright} 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2015",

month = may,

day = "1",

doi = "10.1002/ejic.201500188",

language = "English",

volume = "2015",

pages = "2587--2591",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag GmbH",

number = "15",

}

TY - JOUR

T1 - Syntheses of Ir4(CO)6(η5-C5Me4H)2 and Ir7(μ3-CO)3(CO)12(η5-C5Me5) from pentametallic molybdenum-iridium cluster precursors

AU - Fu, Junhong

AU - Randles, Michael D.

AU - Criddle, Alan L.

AU - Moxey, Graeme J.

AU - Schwich, Torsten

AU - Stranger, Robert

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

PY - 2015/5/1

Y1 - 2015/5/1

N2 - Abstract Reaction of Mo2Ir3(μ-CO)3(CO)6(η5-C5H5)2(η5-C5Me5) with Ir(CO)2(η5-C5Me4H) afforded the four-valence-electron-deficient butterfly cluster Ir4(CO)6(η5-C5Me4H)2; its stability has been rationalized with the aid of density functional theory calculations, which suggest that significant additional intracluster bonding alleviates the formal electron deficiency. Reaction of MoIr4(CO)10(η5-C5H5)(η5-C5Me5) with [N(PPh3)2][Ir(CO)4] afforded the capped octahedral cluster Ir7(μ3-CO)3(CO)12(η5-C5Me5), which possesses three semi-face-capping CO ligands. These outcomes demonstrate that heterometallic clusters may serve as a potential source of new homometallic clusters following appropriate M-M′ cleavage. Reactions of molybdenum-iridium clusters with iridium-containing reagents afforded new homometallic clusters. Ir7(μ3-CO)3(CO)12(η5-C5Me5) possesses three semi-face-capping CO ligands, while Ir4(CO)6(η5-C5Me4H) is formally very electron-deficient; theoretical studies suggest stabilization by significant intracluster multiple Ir-Ir bonding.

AB - Abstract Reaction of Mo2Ir3(μ-CO)3(CO)6(η5-C5H5)2(η5-C5Me5) with Ir(CO)2(η5-C5Me4H) afforded the four-valence-electron-deficient butterfly cluster Ir4(CO)6(η5-C5Me4H)2; its stability has been rationalized with the aid of density functional theory calculations, which suggest that significant additional intracluster bonding alleviates the formal electron deficiency. Reaction of MoIr4(CO)10(η5-C5H5)(η5-C5Me5) with [N(PPh3)2][Ir(CO)4] afforded the capped octahedral cluster Ir7(μ3-CO)3(CO)12(η5-C5Me5), which possesses three semi-face-capping CO ligands. These outcomes demonstrate that heterometallic clusters may serve as a potential source of new homometallic clusters following appropriate M-M′ cleavage. Reactions of molybdenum-iridium clusters with iridium-containing reagents afforded new homometallic clusters. Ir7(μ3-CO)3(CO)12(η5-C5Me5) possesses three semi-face-capping CO ligands, while Ir4(CO)6(η5-C5Me4H) is formally very electron-deficient; theoretical studies suggest stabilization by significant intracluster multiple Ir-Ir bonding.

KW - Cluster compounds

KW - Electron-deficient compounds

KW - Solid-state structures

KW - Synthesis design

KW - Transition metals

UR - http://www.scopus.com/inward/record.url?scp=85028227921&partnerID=8YFLogxK

U2 - 10.1002/ejic.201500188

DO - 10.1002/ejic.201500188

M3 - Article

AN - SCOPUS:85028227921

SN - 1434-1948

VL - 2015

SP - 2587

EP - 2591

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 15

ER -

Syntheses of Ir₄(CO)₆(η⁵-C₅Me₄H)₂ and Ir₇(μ₃-CO)₃(CO)₁₂(η⁵-C₅Me₅) from pentametallic molybdenum-iridium cluster precursors

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