Dynamic Permutational Isomerism in a closo-Cluster

Junhong Fu; Mahbod Morshedi; Graeme J. Moxey; Adam Barlow; Marie P. Cifuentes; Mark G. Humphrey

doi:10.1002/chem.201600550

Dynamic Permutational Isomerism in a closo-Cluster

Junhong Fu, Mahbod Morshedi, Graeme J. Moxey, Adam Barlow, Marie P. Cifuentes, Mark G. Humphrey^*

^*Corresponding author for this work

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

6 Citations (Scopus)

Abstract

Permutational isomers of trigonal bipyramidal [W₂RhIr₂(CO)₉(η⁵-C₅H₅)₂(η⁵-C₅HMe₄)] result from competitive capping of either a W₂Ir or a WIr₂ face of the tetrahedral cluster [W₂Ir₂(CO)₁₀(η⁵-C₅H₅)₂] from its reaction with [Rh(CO)₂(η⁵-C₅HMe₄)]. The permutational isomers slowly interconvert in solution by a cluster metal vertex exchange that is proposed to proceed by Rh-Ir and Rh-W bond cleavage and reformation, and via the intermediacy of an edge-bridged tetrahedral transition state. The permutational isomers display differing chemical and physical properties: replacement of CO by PPh₃ occurs at one permutational isomer only, while the isomers display distinct optical power limiting behavior.

Original language	English
Pages (from-to)	5128-5132
Number of pages	5
Journal	Chemistry - A European Journal
Volume	22
Issue number	15
DOIs	https://doi.org/10.1002/chem.201600550
Publication status	Published - 4 Apr 2016

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@article{579959116d16464d8fcbc8b547eddb5b,

title = "Dynamic Permutational Isomerism in a closo-Cluster",

abstract = "Permutational isomers of trigonal bipyramidal [W2RhIr2(CO)9(η5-C5H5)2(η5-C5HMe4)] result from competitive capping of either a W2Ir or a WIr2 face of the tetrahedral cluster [W2Ir2(CO)10(η5-C5H5)2] from its reaction with [Rh(CO)2(η5-C5HMe4)]. The permutational isomers slowly interconvert in solution by a cluster metal vertex exchange that is proposed to proceed by Rh-Ir and Rh-W bond cleavage and reformation, and via the intermediacy of an edge-bridged tetrahedral transition state. The permutational isomers display differing chemical and physical properties: replacement of CO by PPh3 occurs at one permutational isomer only, while the isomers display distinct optical power limiting behavior.",

keywords = "carbonyl ligands, cluster compounds, heterometallic complexes, isomers, transition metals",

author = "Junhong Fu and Mahbod Morshedi and Moxey, {Graeme J.} and Adam Barlow and Cifuentes, {Marie P.} and Humphrey, {Mark G.}",

note = "Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

month = apr,

day = "4",

doi = "10.1002/chem.201600550",

language = "English",

volume = "22",

pages = "5128--5132",

journal = "Chemistry - A European Journal",

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T1 - Dynamic Permutational Isomerism in a closo-Cluster

AU - Fu, Junhong

AU - Morshedi, Mahbod

AU - Moxey, Graeme J.

AU - Barlow, Adam

AU - Cifuentes, Marie P.

AU - Humphrey, Mark G.

PY - 2016/4/4

Y1 - 2016/4/4

N2 - Permutational isomers of trigonal bipyramidal [W2RhIr2(CO)9(η5-C5H5)2(η5-C5HMe4)] result from competitive capping of either a W2Ir or a WIr2 face of the tetrahedral cluster [W2Ir2(CO)10(η5-C5H5)2] from its reaction with [Rh(CO)2(η5-C5HMe4)]. The permutational isomers slowly interconvert in solution by a cluster metal vertex exchange that is proposed to proceed by Rh-Ir and Rh-W bond cleavage and reformation, and via the intermediacy of an edge-bridged tetrahedral transition state. The permutational isomers display differing chemical and physical properties: replacement of CO by PPh3 occurs at one permutational isomer only, while the isomers display distinct optical power limiting behavior.

AB - Permutational isomers of trigonal bipyramidal [W2RhIr2(CO)9(η5-C5H5)2(η5-C5HMe4)] result from competitive capping of either a W2Ir or a WIr2 face of the tetrahedral cluster [W2Ir2(CO)10(η5-C5H5)2] from its reaction with [Rh(CO)2(η5-C5HMe4)]. The permutational isomers slowly interconvert in solution by a cluster metal vertex exchange that is proposed to proceed by Rh-Ir and Rh-W bond cleavage and reformation, and via the intermediacy of an edge-bridged tetrahedral transition state. The permutational isomers display differing chemical and physical properties: replacement of CO by PPh3 occurs at one permutational isomer only, while the isomers display distinct optical power limiting behavior.

KW - carbonyl ligands

KW - cluster compounds

KW - heterometallic complexes

KW - isomers

KW - transition metals

UR - http://www.scopus.com/inward/record.url?scp=84977867195&partnerID=8YFLogxK

U2 - 10.1002/chem.201600550

DO - 10.1002/chem.201600550

M3 - Article

SN - 0947-6539

VL - 22

SP - 5128

EP - 5132

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 15

ER -

Dynamic Permutational Isomerism in a closo-Cluster

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