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

Chemistry. 2016 Apr 4;22(15):5128-32. doi: 10.1002/chem.201600550. Epub 2016 Feb 29.

Authors

Junhong Fu¹, Mahbod Morshedi¹, Graeme J Moxey¹, Adam Barlow¹, Marie P Cifuentes¹, Mark G Humphrey²

Affiliations

¹ Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia.
² Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia. Mark.Humphrey@anu.edu.au.

PMID: 26868979
DOI: 10.1002/chem.201600550

Abstract

Permutational isomers of trigonal bipyramidal [W2RhIr2(CO)9(η(5)-C5H5)2(η(5)-C5HMe4)] result from competitive capping of either a W2Ir or a WIr2 face of the tetrahedral cluster [W2Ir2(CO)10(η(5)-C5 H5)2] from its reaction with [Rh(CO)2(η(5)-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.

Publication types

Research Support, Non-U.S. Gov't