Dynamic Permutational Isomerism in a closo-Cluster.

Authors :: Fu J
Morshedi M
Moxey GJ
Barlow A
Cifuentes MP
Humphrey MG
Source :: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2016 Apr 04; Vol. 22 (15), pp. 5128-32. Date of Electronic Publication: 2016 Feb 29.
Publication Year :: 2016
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.<br /> (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)