Heterobimetallic rhenium nitrido complexes containing the Kläui tripodal ligand [Co(η(5)-C5H5){P(O)(OEt)2}3](-).

Rhenium nitrido complexes containing the Kläui tripodal ligand [Co(η(5)-C5H5){P(O)(OEt)2}3](-) (LOEt(-)) have been synthesised and their reactions with [Ir(I)(cod)Cl]2 (cod = 1,5-cyclooctadiene) and [Rh(II)2(OAc)4] (OAc(-) = acetate) have been studied. The treatment of [Bu(n)4N][Re(VI)(N)Cl4] with NaLOEt in methanol afforded the Re(VI) nitride [Re(VI)(LOEt)(N)Cl(OMe)] (1). Reactions of 1 with [Ir(I)(cod)Cl]2 and [Rh(II)2(OAc)4] gave the μ-nitrido complexes [(LOEt)(OMe)ClRe(VI)(μ-N)Ir(I)(cod)Cl] (2) and [Rh(II)2(OAc)4{(μ-N)Re(VI)(LOEt)(OMe)Cl}2] (4), respectively. [(LOEt)Cl(PPh3)Re(V)(μ-N)Ir(I)(cod)Cl] (3) and [(LOEt)Cl(PPh3)Re(VI)(μ-N)Ir(I)(cod)Cl][PF6] (3·PF6) have been synthesised from the reactions of [Ir(I)(cod)Cl]2 with [Re(V)LOEt(N)Cl(PPh3)] and [Re(VI)LOEt(N)Cl(PPh3)](PF6), respectively. Similarly, the redox pair [Rh(II)2(OAc)4{(μ-N)Re(V)(LOEt)(PPh3)Cl}2] (5) and [Rh(II)2(OAc)4{(μ-N)Re(VI)(LOEt)(PPh3)Cl}2](PF6)2 (·(PF6)2) have been synthesised from the reactions of [Rh2(OAc)4] with [Re(V)LOEt(N)Cl(PPh3)] and [Re(VI)LOEt(N)Cl(PPh3)](PF6), respectively. While [(LOEt)Cl2Ru(VI)(μ-N)Ir(I)(cod)] (6) was obtained from [Ru(VI)(LOEt)(N)Cl2] and [Ir(I)(cod)Cl]2, the interaction between [Ru(VI)(LOEt)(N)Cl2] and [Rh(II)2(OAc)4] in CH2Cl2 is reversible. The crystal structures of complexes 2, 3, 3·PF6, 5, 5·(PF6)2 and 6 have been determined. X-ray crystallography indicates that the nitrido bridges in 2, 3, 3·PF6 and 6 can be described as MN-Ir (M = Re, Ru) showing Ir-N multiple bond character, whereas the interaction between Re≡N and Rh in 5 and 5·(PF6)2 is mostly of the donor-acceptor type. The electrochemistry of the Re nitrido complexes has been investigated by cyclic voltammetry.