Heterometallic Iridium, Rhodium and Ruthenium Nitrido Complexes Supported by Oxygen and Sulfur Donor Ligands

Heterometallic μ‐nitrido complexes have been synthesized from organometallic complexes containing O/S‐donor ligands and a ruthenium(VI) nitride. The treatment of [Ir(tpip)(L)2] (tpip−=[N(Ph2PO)2]−; L=cyclooctene (coe) or 2,6‐dimethylphenylisocyanide (xylNC)) and [Ir{N(iPr2PS)2}(coe)] with [Ru(LOEt)(N)Cl2] (LOEt−=[Co(η5‐C5H5){P(O)(OEt)2}3]−) (1) afforded [(L)(tpip)Ir(μ‐N)Ru(LOEt)Cl2] (L=coe (2) or xylNC (3)) and [(coe){N(iPr2PS)2}Ir(μ‐N)Ru(LOEt)Cl2] (4), respectively, in which the Ir−N(nitride) bonds show double bond character. The bonding in 2–4 can be described by two resonance forms: Ir(I)−N≡Ru(VI) and Ir(III)=N=Ru(IV). The treatment of [Ph4P][Ir(CO)2Cl2] with 1 afforded (PPh4)[(CO)Cl2Ir(μ‐N)Ru(LOEt)Cl2] (5) that reacted with [Tl(SR)] to give (PPh4)[(CO)(RS)2Ir(μ‐N)Ru(LOEt)Cl2] (R=xyl (6), C6F4H (7)). The reaction of [M(acac)(CO)2)] or [Ru(acac)2(coe)2] (acac−=acetylacetonate) with 1 gave [(CO)(acac)M(μ‐N)Ru(LOEt)Cl2] [M=Ir (8), Rh (9)] or [(H2O)(acac)2Ru(μ‐N)Ru(LOEt)Cl2] (10), whereas the treatment of [Ru(acac)2(MeCN)2] with 1‐azidoadamantane (AdN3) yielded a Ru(II) tetrazene complex, [Ru(acac)2(N4Ad2)] (11). Heterometallic M−N−Ru (M=Ir, Rh, Ru) complexes have been synthesized from the reactions of organometallic complexes containing O/S‐donor ligands with a ruthenium(VI) nitride. X‐ray crystallography indicated that there is extensive π delocalization in the M−N−Ru units. The factors affecting the bonding in the heterometallic nitrido complexes have been studied.