(Nitrido)ruthenium(VI) and -osmium(VI) complexes with catecholate auxiliaries: Synthesis, structure, and conversion into a (phosphoraniminato) osmium(V) complex

Abstract

Treatment of [NnBu4][MVINCl4] (where M = Ru, Os) with catechol (H2Cat) and 3,5-di-tert-butylcatechol (H 2DBCat) in the presence of 2,6-dimethylpyridine (2,6-Me 2Py) gave [NnBu4][MVIN(Cat)2] (where M = Ru 1a, Os 1b) and [2,6-Me2PyH][MVIN(DBCat) 2] (where M = Ru 2a, Os 2b), respectively, n 75-90% yields. Reaction of 2b with triphenylphosphane afforded the (phosphoraniminato)osmium(v) complex [OsV(NPPh3)(DBCat)2(PPh3)] (3) in 90% yield. X-ray crystal structure determinations on 1a, 1b and 3 reveal M=N distances of 1,603(4) and 1.641(8) Å (for 1a and 1b, respectively) and an Os-N(NPPh3) distance of 2.077(3) Å (for 3). The C-O distances in the three complexes range from 1.341(4) to 1.374(7) Å, indicating that the coordinated catecholate ligands adopt the catecholate(2-) state, rather than the semiquinonate(1-) or quinone states. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.