(Nitrido)ruthenium(<scp>VI</scp>) and ‐osmium(<scp>VI</scp>) Complexes with Catecholate Auxiliaries: Synthesis, Structure, and Conversion into a (Phosphoraniminato)osmium(<scp>V</scp>) Complex

Abstract

Abstract Treatment of [N n Bu 4 ][M VI NCl 4 ] (where M = Ru, Os) with catechol (H 2 Cat) and 3,5‐di‐ tert ‐butylcatechol (H 2 DBCat) in the presence of 2,6‐dimethylpyridine (2,6‐Me 2 Py) gave [N n Bu 4 ][M VI N(Cat) 2 ] (where M = Ru 1a , Os 1b ) and [2,6Me 2 PyH][M VI N(DBCat) 2 ] (where M = Ru 2a , Os 2b ), respectively, in 75−90 % yields. Reaction of 2b with triphenylphosphane afforded the (phosphoraniminato)osmium( V ) complex [Os V (NPPh 3 )(DBCat) 2 (PPh 3 )] ( 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(NPPh 3 ) 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 &amp; Co. KGaA, 69451 Weinheim, Germany, 2004)