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

Abstract

Interaction of cis-[Pt(dppm) 2 (O 3 SCF 3 ) 2 ] [dppm = bis(diphenylphosphino)methane], cis-[Pt(Bupy)(O 3 SCF 3 ) 2 ] (Bupy = 4-tert-butylpyridine), [Ir(CO)(PPh 3 ) 2 (O 3 SCF 3 )], and [Rh(cod)(OH 2 )(OTs)] (cod = cycloocta-1,5-diene, OTs = tosylate) with [NBu n 4 ][NOsO 3 ] afforded bimetallic nitrido-bridged complexes cis-[Pt(dppm)(NOsO 3 ) 2 ] 3, trans-[Pt(Bupy) 2 (NOsO 3 ) 2 ] 4, [Ir(CO)(PPh 3 ) 2 (NOsO 3 )] 5 and [{Rh(cod)(NOsO 3 )} 2 ] 6, respectively. Complex 4 crystallises in the P space group with a = 7.936(1), b = 10.758(2), c = 7.738(1) A, α = 100.02(1), β = 99.75(1), γ = 101.75(1)°, U = 622.5(2) A 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 A, respectively. Complex 5 crystallises in the P2 1 /n space group with a = 10.124(1), b = 15.564(2), c = 22.623(3) A, β = 100.08(2)°, U = 3509.7(7) A 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 A, respectively. Treatment of [Au(PPh 3 )(NOsO 3 )] 1 with Ph 3 PNPh gave the N-phosphinimine complex [Au(PPh 3 ){N(PPh 3 )Ph}][NOsO 3 ] 7. Complex 7 crystallises in the P2 1 /n space group with a = 8.780(1), b = 20.781(2), c = 20.711(5) A, β = 91.23(1)°, U = 3788.0(9) A 3 for Z = 4. The Au–N distance is 2.091(8) A and the C–N–P angle in the phosphinimine is 127.0(7)°. Reaction of 1 with Bupy led to substitution of Bupy for [NOsO 3 ] and formation of [Au(PPh 3 )(Bupy)][NOsO 3 ] 8. Reaction of [Pt(dppf)(O 3 SCF 3 )Cl] [dppf = 1,1′-bis(diphenylphosphino)ferrocene] with [NBu n 4 ][NOsO 3 ] afforded the trimetallic complex [Pt(dppf)(NOsO 3 )Cl] 11. Complex 11 crystallizes in the P2 1 /c space group with a = 20.058(2), b = 14.899(1), c = 23.949(2) A, β = 114.57(2)°, U = 6508(1) A 3 for Z = 8. The mean Pt–N, Os–N and Os–O distances are 2.06, 1.66 and 1.67 A, respectively.