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

Article abstract of DOI:10.1016/S0020-1693(99)00096-1

Treatment of Ru(por)(NO)(OTf) (por=dianion of 2,3,7,8,12,13,17,18-octaethylporphyrin H₂(OEP) or 5,10,15,20-tetra(p-tolyl)porphyrin H₂(TTP), OTf=triflate) with [NⁿBu₄][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) A, respectively; the Ru-N-O and Ru-N-Os angles are 153(1) and 138.4(8)°, respectively. Reaction of Ru(por)(NO)(OTf) with [NⁿBu₄][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(Et₂dtc)₂ (Et₂dtc=N,N-diethyldithiocarbamate) afforded the Ru(II)-Re(V) complex (OEP)(NO)RuNRe(Et₂dtc)₂(OTf) (7). Complexes 3 and 4 exhibit porphyrin-centered oxidation along with Os(VIII)-Os(VII) 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.