OSMIUM HYDRAZIDO AND DINITROGEN COMPLEXES

[Os(tpy)(bpy)(NH3)](PF6)(2) (1) was oxidized electrochemically in the presence of a series of amines in aqueous solutions buffered to pH 7. With secondary aliphatic amines, electrolysis gave [Os(tpy)(bpy)(NNR2) ](PF6)(3) (3); number of electrons n = 4.6-5.0, 3 was reduced to [Os(t py)(bpy)(NNR2)](PF6)(2) (2) in aqueous and nonaqueous solutions with n = 1.0, The structures of 2 were determined by X-ray crystallography f or NR2 = diethylamide (2a) and morpholide (2c) and were found to exhib it bent hydrazido(2-) coordination (Os-N-N = 137 degrees), The salts c rystallized in the triclinic system, space group P (1) over bar. For 2 a, a = 9.004(1) Angstrom, b = 9.796(1) Angstrom, c = 20.710(2) Angstro m, alpha = 88.78(2)degrees, beta = 85.43(2)degrees, gamma = 86.22(2)de grees, and Z = 2. For 2c, a = 9.632(8) Angstrom, b = 21.229(9) Angstro m, c 9.039(5) Angstrom, alpha = 97.41(4)degrees, beta = 94.28(5)degree s, gamma = 85.07(5)degrees, and Z = 2. Solutions of 2 were protonated in strongly acidic media to give hydrazido(1-) complexes. The pK(a) of the protonated form of 2a is 0.90 +/- 0.01. Reduction of 2 in aqueous solutions of pH < gave 1 and NH2R2+ with n = 4.0. At higher pH, there is evidence for an Os(II) hydrazine intermediate. Oxidation of 3 by o ne electron afforded transiently stable species which decomposed to gi ve [Os(tpy)(bpy)(NCCH3)](3+) in acetonitrile solution. Pseudo-first-or der rate constants of 8.1 +/- 0.9 s(-1) and 0.200 +/- .005 s(-1) were estimated by cyclic voltammetry on solutions of 2a and 2b (NR2 = piper idide), respectively, Oxidation of 1 at pH 7, in the presence of prima ry aliphatic amines or ammonia, occurred with n = 5.9-6.2, and generat ed [Os-II(tpy)(bpy)(N-2)](PF6)(2) (4).