One-Pot Synthesis of Dihalo(porphyrinato)osmium(IV) Complexes. Evidence for Monohalo(carbonyl)osmium(III) Intermediates
- 1 January 1996
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (25) , 7260-7263
- https://doi.org/10.1021/ic960363t
Abstract
trans-Dichloro-, trans-dibromo-, and trans-diiodoosmium(IV) tetraarylporphyrins were obtained by extremely facile synthetic routes directly from the reactions of the corresponding (carbonyl)osmium(II) complexes with CCl4, CBr4, and CI4, respectively. At short reaction times, appreciable amounts of intermediatesone for each reactionwere observed by spectroscopic investigations. These intermediates were shown to be (carbonyl)(halo)(porphyrinato)osmium(III) complexes by independent preparation of an authentic (carbonyl)(bromo)(porphyrinato)osmium(III) complex, which was identical to the reaction intermediate in the reaction of CBr4 and very similar to those of the other reactions. This provided strong evidence for the reaction mechanism, two stepwise one-electron oxidations of the metal ion. The relatively strong binding of carbon monoxide to osmium(III) is proposed to be an important factor in avoiding dimerization of the reaction intermediates.Keywords
This publication has 13 references indexed in Scilit:
- Nitrous Oxide Activation by a Ruthenium PorphyrinJournal of the American Chemical Society, 1995
- The Highly Efficient Oxidation of Olefins, Alcohols, Sulfides and Alkanes with Heteroaromatic N-Oxides Catalyzed by Ruthenium PorphyrinsHETEROCYCLES, 1995
- A novel facile synthesis of dihalogenoruthenium(IV) porphyrinsJournal of the Chemical Society, Chemical Communications, 1995
- Synthesis and electrochemistry of dialkylosmium-(IV) and -(V) porphyrins. Crystal structure of [Os(ttp)(CH2SiMe3)2][H2ttp = 5,10,15,20-tetra(p-tolyl)porphyrin]J. Chem. Soc., Dalton Trans., 1994
- Synthesis of ruthenium(III) and osmium(III) porphyrin mono-alkyl and -aryl complexes and of a noval six-coordinate asymmetrically substituted ruthenium(IV) porphyrin complex, [Ru(oep)(Ph)(Me)]Journal of the Chemical Society, Chemical Communications, 1994
- Mercaptide complexes of osmium porphyrins. Structure of Os(TTP)(SC6F4H)2Inorganic Chemistry, 1993
- Synthesis and characterization of dihalogenoruthenium(IV) and diphenylruthenium(IV), and phenylruthenium(III) tetraphenylporphyrin complexes, including the crystal structure of Ru(TPP)Br2Inorganic Chemistry, 1991
- Novel osmium(IV) and -(V) porphyrins. Synthesis, spectroscopy, and electrochemistryInorganic Chemistry, 1990
- Synthesis, reactivity, and x-ray structural characterization of trans-dioxoosmium(VI) porphyrin complexesInorganic Chemistry, 1988
- The Crystal and Molecular Structure of Quadrivalent Osmium Porphyrin; μ-Oxo-bis[methoxo(octaethylporphinato)osmium(IV)]Bulletin of the Chemical Society of Japan, 1984