Mixed-metal cluster chemistry. 39. Syntheses and X-ray structures of Mo3Ir3(μ4-η2-CO)(μ3-CO)(CO)10(η5-C5H5)3 and Mo3RhIr3(μ-CO)4(CO)7(η5-C5H5)3(η5-C5Me5)

Junhong Fu; Michael D. Randles; Graeme J. Moxey; Rob Stranger; Marie P. Cifuentes; Mark G. Humphrey

doi:10.1016/j.jorganchem.2016.10.016

Mixed-metal cluster chemistry. 39. Syntheses and X-ray structures of Mo₃Ir₃(μ₄-η²-CO)(μ₃-CO)(CO)₁₀(η⁵-C₅H₅)₃ and Mo₃RhIr₃(μ-CO)₄(CO)₇(η⁵-C₅H₅)₃(η⁵-C₅Me₅)

Junhong Fu, Michael D. Randles, Graeme J. Moxey, Rob Stranger, Marie P. Cifuentes, Mark G. Humphrey^*

^*Corresponding author for this work

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

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Abstract

Thermolysis of tetrahedral Mo₂Ir₂(μ-CO)₃(CO)₇(η⁵-C₅H₅)₂ in refluxing toluene affords small amounts of Mo₃Ir₃(μ₄-η²-CO)(μ₃-CO)(CO)₁₀(η⁵-C₅H₅)₃ (1). Reaction of 1 with Rh(CO)₂(η⁵-C₅Me₅) in refluxing dichloromethane gives Mo₃RhIr₃(μ-CO)₄(CO)₇(η⁵-C₅H₅)₃(η⁵-C₅Me₅) (2) in moderate yield. X-ray diffraction studies show the metal cores adopt edge-bridged trigonal bipyramidal and bicapped trigonal bipyramidal structures, respectively. Cluster 2 is electron precise with 96 CVE, in contrast to the only precedent group 6-group 9 mixed-metal cluster with an identical core geometry, the 94 CVE W₃Ir₄(μ-H)(CO)₁₂(η⁵-C₅H₅)₃ (3). DFT studies have been employed to rationalize the contrasting behavior of 2 and 3. Time-dependent DFT has been employed to assign the key transitions in the linear optical absorption spectrum of 2.

Original language	English
Pages (from-to)	66-70
Number of pages	5
Journal	Journal of Organometallic Chemistry
Volume	829
DOIs	https://doi.org/10.1016/j.jorganchem.2016.10.016
Publication status	Published - 1 Feb 2017

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10.1016/j.jorganchem.2016.10.016

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@article{f41fda22d9bf4b76a2ca640481d62aaf,

title = "Mixed-metal cluster chemistry. 39. Syntheses and X-ray structures of Mo3Ir3(μ4-η2-CO)(μ3-CO)(CO)10(η5-C5H5)3 and Mo3RhIr3(μ-CO)4(CO)7(η5-C5H5)3(η5-C5Me5)",

abstract = "Thermolysis of tetrahedral Mo2Ir2(μ-CO)3(CO)7(η5-C5H5)2 in refluxing toluene affords small amounts of Mo3Ir3(μ4-η2-CO)(μ3-CO)(CO)10(η5-C5H5)3 (1). Reaction of 1 with Rh(CO)2(η5-C5Me5) in refluxing dichloromethane gives Mo3RhIr3(μ-CO)4(CO)7(η5-C5H5)3(η5-C5Me5) (2) in moderate yield. X-ray diffraction studies show the metal cores adopt edge-bridged trigonal bipyramidal and bicapped trigonal bipyramidal structures, respectively. Cluster 2 is electron precise with 96 CVE, in contrast to the only precedent group 6-group 9 mixed-metal cluster with an identical core geometry, the 94 CVE W3Ir4(μ-H)(CO)12(η5-C5H5)3 (3). DFT studies have been employed to rationalize the contrasting behavior of 2 and 3. Time-dependent DFT has been employed to assign the key transitions in the linear optical absorption spectrum of 2.",

keywords = "Carbonyl, Cluster, Iridium, Molybdenum, Rhodium",

author = "Junhong Fu and Randles, {Michael D.} and Moxey, {Graeme J.} and Rob Stranger and Cifuentes, {Marie P.} and Humphrey, {Mark G.}",

note = "Publisher Copyright: {\textcopyright} 2016 Elsevier B.V.",

year = "2017",

month = feb,

day = "1",

doi = "10.1016/j.jorganchem.2016.10.016",

language = "English",

volume = "829",

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T1 - Mixed-metal cluster chemistry. 39. Syntheses and X-ray structures of Mo3Ir3(μ4-η2-CO)(μ3-CO)(CO)10(η5-C5H5)3 and Mo3RhIr3(μ-CO)4(CO)7(η5-C5H5)3(η5-C5Me5)

AU - Fu, Junhong

AU - Randles, Michael D.

AU - Moxey, Graeme J.

AU - Stranger, Rob

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

PY - 2017/2/1

Y1 - 2017/2/1

N2 - Thermolysis of tetrahedral Mo2Ir2(μ-CO)3(CO)7(η5-C5H5)2 in refluxing toluene affords small amounts of Mo3Ir3(μ4-η2-CO)(μ3-CO)(CO)10(η5-C5H5)3 (1). Reaction of 1 with Rh(CO)2(η5-C5Me5) in refluxing dichloromethane gives Mo3RhIr3(μ-CO)4(CO)7(η5-C5H5)3(η5-C5Me5) (2) in moderate yield. X-ray diffraction studies show the metal cores adopt edge-bridged trigonal bipyramidal and bicapped trigonal bipyramidal structures, respectively. Cluster 2 is electron precise with 96 CVE, in contrast to the only precedent group 6-group 9 mixed-metal cluster with an identical core geometry, the 94 CVE W3Ir4(μ-H)(CO)12(η5-C5H5)3 (3). DFT studies have been employed to rationalize the contrasting behavior of 2 and 3. Time-dependent DFT has been employed to assign the key transitions in the linear optical absorption spectrum of 2.

AB - Thermolysis of tetrahedral Mo2Ir2(μ-CO)3(CO)7(η5-C5H5)2 in refluxing toluene affords small amounts of Mo3Ir3(μ4-η2-CO)(μ3-CO)(CO)10(η5-C5H5)3 (1). Reaction of 1 with Rh(CO)2(η5-C5Me5) in refluxing dichloromethane gives Mo3RhIr3(μ-CO)4(CO)7(η5-C5H5)3(η5-C5Me5) (2) in moderate yield. X-ray diffraction studies show the metal cores adopt edge-bridged trigonal bipyramidal and bicapped trigonal bipyramidal structures, respectively. Cluster 2 is electron precise with 96 CVE, in contrast to the only precedent group 6-group 9 mixed-metal cluster with an identical core geometry, the 94 CVE W3Ir4(μ-H)(CO)12(η5-C5H5)3 (3). DFT studies have been employed to rationalize the contrasting behavior of 2 and 3. Time-dependent DFT has been employed to assign the key transitions in the linear optical absorption spectrum of 2.

KW - Carbonyl

KW - Cluster

KW - Iridium

KW - Molybdenum

KW - Rhodium

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U2 - 10.1016/j.jorganchem.2016.10.016

DO - 10.1016/j.jorganchem.2016.10.016

M3 - Article

SN - 0022-328X

VL - 829

SP - 66

EP - 70

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Mixed-metal cluster chemistry. 39. Syntheses and X-ray structures of Mo₃Ir₃(μ₄-η²-CO)(μ₃-CO)(CO)₁₀(η⁵-C₅H₅)₃ and Mo₃RhIr₃(μ-CO)₄(CO)₇(η⁵-C₅H₅)₃(η⁵-C₅Me₅)

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