Issue 13, 2000

Carbonylcyanometalates as building blocks: heterometallic complexes containing Mn(μ-C[triple bond, length as m-dash]N)M (M = Cu, Au, Ni, Pd or Pt), Mn(μ-C[triple bond, length as m-dash]N)Pd(μ-dppm)2Mn and Mn(μ-C[triple bond, length as m-dash]N)M(μ-dppm)2Pd(μ-N[triple bond, length as m-dash]C)Mn (M = Pt or Pd) chains of atoms and crystal structure of the mixed-metal cluster [Ru3{(μ3-NC)MnCp(CO)2}(μ-AuPPh3)(CO)10]

Abstract

A comparison between the products obtained by reaction of the isosteric metalates [MoCp(CO)3] (Cp = η5-C5H5) and [MnCp(or Cp′)(CN)(CO)2] (Cp′ = η5-C5H4Me) with various mono- or poly-nuclear complexes of Cu, Au, Ni, Pd, Pt or Ru showed that the metal-centered basicity of the former leads to metal–metal bonding whereas the dominant σ-donor properties of the CN ligand in the latter preferentially lead to the formation of cyanide bridges between the metal centres. Only in the case of the unusual heterometallic octanuclear cluster [(OC)Pd(μ-NC)MnCp′(CO)2]4 were direct metal–metal bonding and CN-bridge formation observed. The crystal structure of [Ru3{(μ3-NC)MnCp(CO)2}(μ-AuPPh3)(CO)10] was shown by X-ray diffraction to consist of a Ru3Au butterfly whose Ru–Ru hinge is bridged by the N-bonded NCMnCp(CO)2 fragment. Controlled thermolysis of the octanuclear cluster [(OC)Pd(μ-NC)MnCp′(CO)2]4 led to the formation of bimetallic particles.

Supplementary files

Article information

Article type
Paper
Submitted
22 Mar 2000
Accepted
05 May 2000
First published
06 Jun 2000

J. Chem. Soc., Dalton Trans., 2000, 2195-2203

Carbonylcyanometalates as building blocks: heterometallic complexes containing Mn(μ-C[triple bond, length as m-dash]N)M (M = Cu, Au, Ni, Pd or Pt), Mn(μ-C[triple bond, length as m-dash]N)Pd(μ-dppm)2Mn and Mn(μ-C[triple bond, length as m-dash]N)M(μ-dppm)2Pd(μ-N[triple bond, length as m-dash]C)Mn (M = Pt or Pd) chains of atoms and crystal structure of the mixed-metal cluster [Ru3{(μ3-NC)MnCp(CO)2}(μ-AuPPh3)(CO)10]

P. Braunstein, B. Oswald, A. Tiripicchio and F. Ugozzoli, J. Chem. Soc., Dalton Trans., 2000, 2195 DOI: 10.1039/B002292F

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