Syntheses and crystal structures of bi- and tri-metallic complexes containing a trioxoosmium(VIII) moiety

Interaction of cis-[Pt(dppm)2(O3SCF3)2] [dppm = bis(diphenylphosphino)methane], cis-[Pt(Bupy)(O3SCF3)2] (Bupy = 4-tert-butylpyridine), [Ir(CO)(PPh3)2(O3SCF3)], and [Rh(cod)(OH2)(OTs)] (cod = cycloocta-1,5-diene, OTs = tosylate) with [NBun4][NOsO3] afforded bimetallic nitrido-bridged complexes cis-[Pt(dppm)(NOsO3)2] 3, trans-[Pt(Bupy)2(NOsO3)2] 4, [Ir(CO)(PPh3)2(NOsO3)] 5 and [{Rh(cod)(NOsO3)}2] 6, respectively. Complex 4 crystallises in the P1 space group with a = 7.936(1), b = 10.758(2), c = 7.738(1) Å, α = 100.02(1), β = 99.75(1), γ = 101.75(1)°, U = 622.5(2) Å3for Z = 1. The Pt-N (Os), Os-N and the mean Os-O distances are 1.958(7), 1.681(7) and 1.724 Å, respectively. Complex 5 crystallises in the P21/n space group with a = 10.124(1), b = 15.564(2), c = 22.623(3) Å, β = 100.08(2)°, U = 3509.7(7) Å3for Z = 4. The Ir-N, Os-N and the mean Os-O distances are 1.998(7), 1.710(7) and 1.718 Å, respectively. Treatment of [Au(PPh3)(NOsO3)] 1 with Ph3P=NPh gave the N-phosphinimine complex [Au(PPh3){N(=PPh3)Ph}][NOsO3] 7. Complex 7 crystallises in the P21/n space group with a = 8.780(1), b = 20.781(2), c = 20.711(5) Å, β = 91.23(1)°, U = 3788.0(9) Å3for Z = 4. The Au-N distance is 2.091(8) Å and the C-N-P angle in the phosphinimine is 127.0(7)°. Reaction of 1 with Bupy led to substitution of Bupy for [NOsO3] and formation of [Au(PPh3)(Bupy)][NOsO3] 8. Reaction of [Pt(dppf)(O3SCF3)Cl] [dppf = 1,1′-bis(diphenylphosphino)ferrocene] with [NBun4][NOsO3] afforded the trimetallic complex [Pt(dppf)(NOsO3)Cl] 11. Complex 11 crystallizes in the P21/c space group with a = 20.058(2), b = 14.899(1), c = 23.949(2) Å, β = 114.57(2)°, U = 6508(1) Å3for Z = 8. The mean Pt-N, Os-N and Os-O distances are 2.06, 1.66 and 1.67 Å, respectively.