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 [NBu(4)(n)l[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 P (1) over bar space group with a = 7.936(1), b = 10.758(2), c = 7.738(1) Angstrom, alpha = 100,02(1), beta = 99.75(1), gamma = 101.75(1)degrees, U=622.5(2) Angstrom(3) for Z = 1. The Pt-N (Os), Os-N and the mean Os-O distances are 1.958(7), 1.681(7) and 1.724 Angstrom, respectively. Complex 5 crystallises in the P2(1)/n space group with a = 10.124(1). b = 15.564(2), c = 22.623(3) Angstrom, beta = 100.08(2)degrees, U = 3509.7(7) Angstrom(3) for Z = 4. The Ir-N, Os-N and the mean Os-O distances are 1.998(7) 1.710(7) and 1.718 Angstrom, respectively. Treatment of [Au(PPh3)(NOsB3)] 1 with Ph3P=NPh gave the N-phosphinimine complex [Au(PPh3){N(=PPh3)Ph}][NOsO3] 7. Complex 7 crystallises in the P2(1)/n space: group with a = 8.780(1), b = 20.781(2), c = 20.711(5) Angstrom, beta = 91.23(1)degrees, U = 3788.0(9) Angstrom(3) for Z = 4. The Au-N distance is 2.091(8) Angstrom and the C-N-P angle in the phosphinimine is 127.0(7)degrees. 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 [NBuO4n][NOsO3] afforded the trimetallic complex [Pt(dppf)(NOsO3)Cl] 11. Complex 11 crystallizes in the P2(1)/c space group with a = 20.058(2), b = 14.899(1), c = 23.943(1) Angstrom, beta = 114.57(2)degrees, U = 6508(1) Angstrom(3) for Z = 8. The mean Pt-N, Os-N and Os-O distances are 2.06, 1.66 and 1.67 Angstrom, respectively.