One-pot synthesis of cis-bis(2,2'-bipyridine) carbonylruthenium(II) complexes from a carbonato precursor: X-ray crystal structures and electron transfer processes of the series complexes

摘要

The reaction of Bransted acids with cis-[Ru(bpy)_2(CO_3)] (bpy = 2,2'-bipyridine) under CO results in cleavage of the carbonato ligand and formation of cationic cis-[Ru(bpy)_2(CO)L]~(n+) complexes [L = ONO_2 (1~+), OH_2 (2~(2+)), Cl (3~+), OCOH (4~+), and OCOCH_3 (5~+)]. The structures of 1~+ and 2~(2+) were confirmed by single-crystal X-ray diffraction. Crystal data for 1(PF_6): monoclinic, P2_1/c, a = 10.5242(3), b = 15.4727(3), c= 14.6571(3) A, β = 92.3219(9)°, V= 2384.77(9) A~3, Z = 4, D_(calcd) = 1.806 g cm~(-3), 5460 unique reflections (R_(int)= 0.032), R_1 =0.0540 [I>2σ(I)], wR_2 = 0.1642 (all reflections);;crystal data for 2(ClO_4)_2 . H_2O: mono-clinic, C2/c, a = 20.4247(7), b = 10.0777(3), c= 15.6039(5) A, β= 127.7569(8)°, V=2539.31(14) A~3, Z = 4, D_(calcd) = 1.769 g cm~(-3), 2895 unique reflections (R_(int) = 0.036), R_1 = 0.0343 [I > 2σ(I)], wR_2 = 0.0907 (all reflections). Except for 2(PF_6)_2 the complexes exhibit oxidation at 1.02-1.30 V versus Fc~+/Fc in acetonitrile. Bipyridine-centered reductions are also observed;;these redox potentials depend on the nature of L. This convenient synthesis will be useful for producing cis-[Ru(bpy)_2(CO)L]~(n+)-type complexes in high yield.