Heterobimetallic nitrido-bridged Ru(II)NOs(VIII) and Ru(II)NOs(VI) complexes containing ruthenium porphyrins

Treatment of Ru(por)(NO)(OTf) (por=dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin H-2(OEP) or 5,10,15,20-tetra(p-tolyl)porphyrin H-2(TTP), OTf=triflate) with [(NBu4)-Bu-n][OsO3N] afforded the nitrido-bridged Ru(II)-Os(VIII) complexes [(por)(NO)RuNOsO3] (por=OEP (3) or TTP (4)). The structure of 3 has been established by X-ray crystallography. The Ru-N(O), Ru-N(Os and Os-N distances in 3 are 1.83(2, 2.03(1) and 1.79(1) Angstrom, respectively; the Ru-N-O and Ru-N-Os angles are 153(1) and 138.4(8)degrees, respectively. Reaction of Ru(por)(NO)(OTf) with [(NBu4)-Bu-n]OsNL2] (H2L = 3,4-toluenedithiol) gave the nitrido-bridged Ru(II)-Os(VI) complexes (por)(NO)RuNOsL2 (por = OEP (5), TTP (6)). Treatment of Ru(OEP)(NO)(OTf) with ReN(Et(2)dtc)(2) (Et(2)dtc = N,N-diethyldithiocarbamate) afforded the Ru(IT)-Re(V) complex (OEP)(NO)RuNRe(Et(2)dtc)(2)(OTf) (7). Complexes 3 and 4 exhibit porphyrin-centered oxidation along with Os(VIII)-Os(VIT) and Ru(II)-Ru(I) reductions. Complexes 5 and 6 exhibit Os(VII)-Os(VI) and porphyrin ring oxidation along with Ru(II)-Ru(I) reduction. (C) 1999 Elsevier Science S.A. All rights reserved.