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

Abstract

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 P1̄ 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) ų 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 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) ų for 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}][NOsO ₃] 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) ų for 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) ų for Z = 8. The mean Pt–N, Os–N and Os–O distances are 2.06, 1.66 and 1.67 Å, respectively.

References

1. R. Criegee, Justus Liebigs Ann. Chem., 1936, 522, 75; M. Schröder, Chem. Rev., 1980, 80, 107 and refs. Therein W. B. Motherwell and A. S. Williams, Angew. Chem., Int. Ed. Engl., 1995, 34, 2031.
2. K. B. Sharpless, D. W. Patrick, L. K. Truesdale and S. A. Biller, J. Am. Chem. Soc., 1975, 97, 2305; K. B. Sharpless, A. O. Chong and K. Oshima, J. Org. Chem., 1976, 41, 177.
3. H. C. Holb, M. S. VanNieuwenhze and K. B. Sharpless, Chem. Rev., 1994, 94, 2483 and refs. therein.
4. G. Liu, H. T. Chang and K. B. Sharpless, Angew. Chem., Int. Ed. Engl., 1996, 35, 45; J. Rudolph, P. C. Sennhenn, C. P. Vlaar and K. B. Sharpless, Angew. Chem., Int. Ed. Engl., 1996, 35, 2810; G. Li, H. H. Angert and K. B. Sharpless, Angew. Chem., Int. Ed. Engl., 1996, 35, 2813.
5. W.-H. Leung, J. L. C. Chim and W.-T. Wong, J. Chem. Soc., Dalton Trans., 1996, 3153.
6. A. F. Clifford and C. S. Kobayashi, Inorg. Synth., 1960, 6, 204.
7. G. B. Kauffamn, Inorg. Synth., 1963, 7, 249.
8. M. P. Brown, R. J. Puddephatt, M. Rashidi and K. R. Seddon, J. Chem. Soc., Dalton Trans., 1977, 951.
9. J. P. Collman and M. Kubota, Inorg. Synth., 1990, 28, 92.
10. U. Kölle, R. Görissen and T. Wagner, Chem. Ber., 1995, 128, 911.
11. D. A. Clemente, G. Pilloni, B. Corain, B. Longato and M. Tiripicchio-Camellini, Inorg. Chim. Acta, 1986, 115, L9.
12. N. W. Hoffman, N. Prokopuk, M. J. Robbins, C. M. Jones and N. M. Doherty, Inorg. Chem., 1991, 30, 4177.
13. M. Rahim and K. J. Ahmed, Organometallics, 1994, 13, 1751.
14. G. J. Leigh and R. L. Richards, in Comprehensive Organometallic Chemistry, eds. G. Wilkinson, F. G. A. Stone and E. W. Abel, Pergamon, Oxford, vol. 5, p. 543.
15. D. J. Berrisford, C. Bolm and K. B. Sharpless, Angew. Chem., Int. Ed. Engl., 1995, 34, 1059.
16. C. A. Reed and W. R. Roper, J. Chem. Soc., Dalton Trans., 1973, 1370.
17. W. A. Nugent and J. M. Mayer, Metal-Ligand Multiple Bonds, Wiley, New York, 1988, p. 126.
18. B. S. McGilligan, J. Arnold, G. Wilkinson, B. Hussain-Bates and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1990, 2465.
19. K. Dehnicke and J. Strähle, Angew. Chem., Int. Ed. Engl., 1992, 31, 955.
20. W. Kafitz, F. Weller and K. Dehnicke, Z. Anorg. Allg. Chem., 1982, 590, 175.