Abstract
AbstractTreatment of [NnBu4][MVINCl4] (where M = Ru, Os) with catechol (H2Cat) and 3,5‐di‐tert‐butylcatechol (H2DBCat) in the presence of 2,6‐dimethylpyridine (2,6‐Me2Py) gave [NnBu4][MVIN(Cat)2] (where M = Ru 1a, Os 1b) and [2,6Me2PyH][MVIN(DBCat)2] (where M = Ru 2a, Os 2b), respectively, in 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)
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