View PDF Version
 
DOI: 10.1039/A800762D (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 1905-1912

Zinc, cadmium and mercury complexes of redox-active cyanomanganese carbonyl ligands: intramolecular electron transfer through tetrahedral d10 metal centres[hair space]

(Note: The full text of this document is currently only available in the PDF Version )

Neil G. Connelly, Gareth R. Lewis, M. Teresa Moreno and A. Guy Orpen

Abstract

The redox-active cyanomanganese carbonyl ligands cis- and trans-[Mn(CN)(CO)2{P(OR)3}(dppm)] (R = Ph or Et, dppm = Ph2PCH2PPh2) reacted with ZnBr2, CdI2 and Hg(NO3)2 to give the tetrahedral (at M) complexes [X2M{(µ-NC)MnLx}2] [MX2 = ZnBr2, CdI2 or Hg(NO3)2; Lx = cis- or trans-(CO)2{P(OR)3}(dppm); R = Ph or Et]; similarly [Mn(CN)(NO)(PPh3)(η-C5H4Me)] gives [X2M{(µ-NC)MnLx}2] {MX2 = ZnBr2 or CdI2, Lx = (NO)(PPh3)(η-C5H4Me)}. Treatment of [Br2Zn{(µ-NC)MnLx}2] [Lx = trans-(CO)2{P(OEt)3}(dppm)] 4 with TlPF6 in the presence of 1 or 2 equivalents of trans-[Mn(CN)(CO)2{P(OEt)3}(dppm)] gave the tetra- and penta-metallic complexes [BrZn{(µ-NC)MnLx}3][PF6] 13 and [Zn{(µ-NC)MnLx}4][PF6]2 14 [Lx = trans-(CO)2{P(OEt)3}(dppm)] respectively. Differential pulse volammetry showed that 4, 13 and 14 are oxidised to weakly interacting mixed-valence complexes. The reaction of trans-[Mn(CN)(CO)(dppm)2] with ZnBr2 or CdX2 (X = Br or I) in thf gave the bimetallic species [X2(thf[hair space])M(µ-NC)Mn(CO)(dppm)2] (MX2 = ZnBr2 or CdI2) and [Br2Cd(µ-NC)Mn(CO)(dppm)2] which are oxidised by [Fe(η-C5H5)2][PF6] to the MnII complexes [X2(thf[hair space])M(µ-NC)Mn(CO)(dppm)2][PF6] and [Br2Cd(µ-NC)Mn(CO)(dppm)2][PF6]. The crystal structures of the tetrahedral polynuclear complexes [I2Cd{(µ-NC)MnLx}2] [Lx = trans-(CO)2{P(OEt)3}(dppm)] 9 and [Br2(thf[hair space])Zn(µ-NC)Mn(CO)(dppm)2] 15 are reported, and the importance of steric effects (as quantified by cone angles) in the behaviour of cyanomanganese carbonyl ligands is noted.

References

  1. H. Vahrenkamp, A. Geiss and G. N. Richardson, J. Chem. Soc., Dalton Trans., 1997, 3643 RSC.
  2. T. Iwamoto, S. Nishikiori, T. Kitazawa and H. Yuge, J. Chem. Soc., Dalton Trans., 1997, 4127 RSC.
  3. K. R. Dunbar and R. A. Heintz, Prog. Inorg. Chem., 1997, 45, 283 CAS.
  4. N. G. Connelly, K. A. Hassard, B. J. Dunne, A. G. Orpen, S. J. Raven, G. A. Carriedo and V. Riera, J. Chem. Soc., Dalton Trans., 1988, 1623 RSC.
  5. G. A. Carriedo, V. Riera, N. G. Connelly and S. J. Raven, J. Chem. Soc., Dalton Trans., 1987, 1769 RSC.
  6. D. L. Reger, D. J. Fauth and M. D. Dukes, J. Organomet. Chem., 1979, 170, 217 CrossRef CAS.
  7. F. L. Atkinson, A. Christofides, N. G. Connelly, H. J. Lawson, A. C. Loyns, A. G. Orpen, G. M. Rosair and G. H. Worth, J. Chem. Soc., Dalton Trans., 1993, 1441 RSC.
  8. N. C. Brown, G. B. Carpenter, N. G. Connelly, J. G. Crossley, A. Martin, A. G. Orpen, A. L. Rieger, P. H. Rieger and G. H. Worth, J. Chem. Soc., Dalton Trans., 1996, 3977 RSC.
  9. F. Bombin, G. A. Carriedo, J. A. Miguel and V. Riera, J. Chem. Soc., Dalton Trans., 1981, 2049 RSC; A. M. Bond, R. Colton and M. J. McCormick, Inorg. Chem., 1977, 16, 155 CrossRef CAS; A. M. Bond, B. S. Grabaric and Z. Grabaric, Inorg. Chem., 1978, 17, 1013 CrossRef CAS.
  10. N. G. Connelly, S. J. Raven, G. A. Carriedo and V. Riera, J. Chem. Soc., Chem. Commun., 1986, 992 RSC.
  11. International Tables for Crystallography, Kluwer, Dordrecht, 1992, vol. C Search PubMed.
  12. B. F. Hoskins and R. Robson, J. Am. Chem. Soc., 1990, 112, 1546 CrossRef CAS.
  13. N. G. Connelly, O. M. Hicks, G. R. Lewis, M. T. Moreno and A. G. Orpen, following paper.
  14. F. L. Atkinson, N. C. Brown, N. G. Connelly, A. G. Orpen, A. L. Rieger, P. H. Rieger and G. M. Rosair, J. Chem. Soc., Dalton Trans., 1996, 1959 RSC.
  15. G. A. Carriedo, N. G. Connelly, E. Perez-Carreno, A. G. Orpen, A. L. Rieger, P. H. Rieger, V. Riera and G. M. Rosair, J. Chem. Soc., Dalton Trans., 1993, 3103 RSC.
  16. G. A. Carriedo, N. G. Connelly, M. C. Crespo, I. C. Quarmby, V. Riera and G. H. Worth, J. Chem. Soc., Dalton Trans., 1991, 315 RSC.
  17. G. A. Carriedo, M. C. Crespo, V. Riera, M. G. Sanchez, M. L. Valin, D. Moreiras and X. Solans, J. Organomet. Chem., 1986, 302, 47 CrossRef CAS.
  18. A. Christofides, N. G. Connelly, H. J. Lawson, A. C. Loyns, A. G. Orpen, M. O. Simmonds and G. H. Worth, J. Chem. Soc., Dalton Trans., 1991, 1595 RSC.
  19. J. C. Smart and B. L. Pinsky, J. Am. Chem. Soc., 1980, 102, 1009 CrossRef CAS; N. G. Connelly and W. E. Geiger, Chem. Rev., 1996, 96, 877 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.