Preparation and characterization of some ruthenium(III) porphyrins, including the crystal structure of bromo(octaethylporphinato)(triphenylphosphine)ruthenium(III)

• Published in: Canadian journal of chemistry 1984, Vol.62 (7), p.1238-1245
• Main Authors: JAMES, B. R, DOLPHIN, D, LEUNG, T. W, EINSTEIN, F. W. B, WILLIS, A. C
• Format: Article
• Language: English
• Subjects: Bioinorganic chemistry; Chemistry; Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Inorganic chemistry and origins of life; Inorganic compounds; Metal complexes; Physics; Structure of solids and liquids; crystallography; Structure of specific crystalline solids
• ISSN: 0008-4042; 1480-3291

Some ruthenium(III) complexes Ru(porp)(L)X and (Ru(porp)L sub(2))X, (porp = dianion of octaethylporphyrin (OEP) or tetraphenylporphyrin (TPP); L = PPh sub(3), P super(n)Bu sub(3); X = Br, Cl) have been prepared from the precursor complexes Ru(porp)L sub(2) or Ru(porp)(CO)L using as oxidant the halogens, or air in the presence of the hydrogen halides. The X = PF sub(6) salts can be made using Et sub(3)O super(+)PF sub(6) super(-) as oxidant. Ruthenium(II) porphyrin pi -cation radical intermediates have sometimes been detected. The X-ray crystal structure of Ru(OEP)(PPh sub(3))Br, the first reported for a ruthenium(III) porphyrin, reveals that metal is displaced 0.049 Angstrom from the plane of the pyrrole N atoms towards the phosphine. The Ru(OEP)(py)Br and (Ru(OEP)(py)CH sub(3)CN)PF sub(6) 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 super(1)H nmr data, the latter showing large paramagnetic shifts, are also presented.