By M. Bacci, J. Fischer, M.H. Gubelmann, B. Koren, F. Mathey, M. Melnik, J.H. Nelson, P. Sivy, F. Valach, A.F. Williams

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Replacement of the axial imidazole ligand trans to dioxygen by CH3S- to give a model for cytochrome P 450271) is accompanied by the observation of ~t donation from sulphur to iron. DioxygenComplexesof the Transition Metals 27 Veillard and co-workers have published ab initio LCAO SCF calculations on dioxygen iron porphyrins with varying axial ligands 262'272,273). They find little change on substituting ammonia by imidazole as the axial ligand. The interaction of the in-plane ~r~ orbital is essentially with the dy~ orbital (a type (ii) overlap, Fig.

Apart from the references given above and those in the reviews, we may also mention the studies on spectra of doubly bridged r/1 : r/1 dioxygen complexes of cobalt by Fallab and his group94'303,435,438)and the detailed studies of biological complexes such as oxyhaemoglobin3°4), oxymyoglobin3°s) and haemerythrin3°6). Vibrational Spectra. In his review4) Vaska discussed the dioxygen stretching frequencies measured in dioxygen complexes, and showed how the values then known fell into two groups. For r/1 and r/l:r/1 superoxo complexes the frequencies lay in the range 1075--1195 cm -1 and for r/2 and r/1 : r/1 peroxo complexes in the range 790-932 cm -1.

The transition excited in this photolysis is thought to be iridium to phosphine charge transfer. No formation of singlet molecular oxygen could be detected. (Ph3P)2PdO2 is photolysed in dichloromethane solution to give c/s (Ph3P)PdC12; no singlet molecular oxygen could be detected. The transition excited is thought to have essentially dioxygen-metal charge transfer character433). H. Gubelmann and A. F. Williams tion excited is thought to be similar to that for (Ph3P)PdO 2 and it is difficult to see why ringlet oxygen is produced in one case and not in the other; this may conceivably be a result of the different methods used to detect its formation.

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Transition Metal Complexes Structures and Spectra by M. Bacci, J. Fischer, M.H. Gubelmann, B. Koren, F. Mathey, M. Melnik, J.H. Nelson, P. Sivy, F. Valach, A.F. Williams


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