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Photochemical reaction of CpIr(CO)2 with C6F 5X (X = CN, F): Formation of diiridium(II) complexes
K.H.G. Mak, P.K. Chan, W.Y. Fan, , W.K. Leong
Published in
Volume: 32
Issue: 4
Pages: 1053 - 1059
Visible light irradiation of CpIr(CO)2 (1) in pentafluorobenzontrile resulted in the formation of the two isomeric diiridium(II) complexes [CpIr(μ-CO)(C6F4CN)] 2 (3) and [CpIr(CO)(C6F4CN)]2 (4), while the analogous reaction of 1 in hexafluorobenzene to give [CpIr(μ-CO)(C6F5)]2 (3a) required UV irradiation. Complex 4 isomerizes to 3 under visible light irradiation. A reaction pathway to 4 involving aromatic nucleophilic substitution has been proposed on the basis of experimental and computational data. The isomerization of 4 to 3 is believed to proceed via a radical species resulting from homolytic fission of the Ir-Ir bond. © 2013 American Chemical Society.
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