Author:
James Brian R.,Dolphin David,Leung T. W.,Einstein Frederick W. B.,Willis Anthony C.
Abstract
Some ruthenium(III) complexes Ru(porp)(L)X and [Ru(porp)L2]X, (porp = dianion of octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP); L = PPh3, P″Bu3; X = Br, Cl) have been prepared from the precursor complexes Ru(porp)L2 or Ru(porp)(CO)L using as oxidant the halogens, or air in the presence of the hydrogen halides. The X = PF6 salts can be made using Et3O+PF6− as oxidant. Ruthenium(II) porphyrin π-cation radical intermediates have sometimes been detected. The X-ray crystal structure of Ru(OEP)(PPh3)Br, the first reported for a ruthenium(III) porphyrin, reveals that metal is displaced 0.049 Å from the plane of the pyrrole N atoms towards the phosphine. The Ru(OEP)(py) Br and [Ru(OEP)(py)CH3CN]PF6 complexes have been synthesized from Ru(OEP)(CO)py. The ruthenium(III) complexes are low-spin as shown by magnetic and esr data. Optical and 1H nmr data, the latter showing large paramagnetic shifts, are also presented.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
31 articles.
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