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

Heterometallic mu-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(iPr(2)PS)(2)}(coe)] with [Ru-(L-OEt)(N)Cl-2] (L-OEt(-) = [Co(eta(5)-C5H5){P(O)(OEt)(2)}(3)](-)) (1) afforded [(L)(tpip)Ir(mu-N)Ru(L-OEt)Cl-2] (L = coe (2) or xyINC (3)) and [(coe){N-(iPr(2)PS)(2)}Ir(mu-N)Ru(L-OEt)Cl-2] (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(1) N Ru(VI) and Ir(III) = N=Ru(IV). The treatment of [Ph4P][Ir(CO)(2) Cl-2] with 1 afforded (PPh4)[(CO)Cl2Ir(mu-N)Ru(L-OEt)Cl-2] (5) that reacted with [TI(SR)] to give (PPh4)[(CO)(RS)(2)Ir(mu-N)Ru(L-OEt)Cl-2] (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(mu-N)Ru(L-OEt)Cl-2 ] [M=Ir (8), Rh (9)] or [(H2O)(acac)(2) Ru(mu-N)Ru(L-OEt)Cl-2] (10), whereas the treatment of [Ru(acac)(2)(MeCN)(2)] with 1-azidoadamantane (AdN(3)) yielded a Ru(II) tetrazene complex, [Ru(acac)(2)(N(4)Ad)] (11).