The synthesis, chemical behavior and single crystal X ray structure of two new Co/Ni bimetallic carbide clusters, namely [Co2Ni10(CO)20C]2− and [Co3Ni9(CO)20C]2−, are reported. The first complex was isolated in ca. 30% yield among the products of the reaction of Co3(CO)9CCl with [Ni6(CO)12]2−, while the second was obtained quantitatively by reaction with protonic acids of the previously reported [Co3Ni9(CO)20C]3−. The two compounds are isostructural and show a metal frame which can be regarded as derived by distortion of a tetra-capped triangulated dodecahedron of D2d symmetry; the statistical (Co and Ni atoms being undistinguishable) idealized symmetry of the metal frame is only D2 owing to progressive deformations toward a tetra-capped tetragonal antiprismatic geometry, which are probably related to the steric requirements of the interstitial carbide atom.
Ceriotti, A., DELLA PERGOLA, R., Longoni, G., Manassero, M., Masciocchi, N., Sansoni, M. (1987). Bimetallic Co-Ni Carbide Clusters: Synthesis and Crystal-Structure of the [CO2NI10(CO)20C]2- and [CO3NI9(CO)20C]2- DIANIONS. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 330(1-2), 237-252 [10.1016/0022-328X(87)80291-7].
Bimetallic Co-Ni Carbide Clusters: Synthesis and Crystal-Structure of the [CO2NI10(CO)20C]2- and [CO3NI9(CO)20C]2- DIANIONS
DELLA PERGOLA, ROBERTO;
1987
Abstract
The synthesis, chemical behavior and single crystal X ray structure of two new Co/Ni bimetallic carbide clusters, namely [Co2Ni10(CO)20C]2− and [Co3Ni9(CO)20C]2−, are reported. The first complex was isolated in ca. 30% yield among the products of the reaction of Co3(CO)9CCl with [Ni6(CO)12]2−, while the second was obtained quantitatively by reaction with protonic acids of the previously reported [Co3Ni9(CO)20C]3−. The two compounds are isostructural and show a metal frame which can be regarded as derived by distortion of a tetra-capped triangulated dodecahedron of D2d symmetry; the statistical (Co and Ni atoms being undistinguishable) idealized symmetry of the metal frame is only D2 owing to progressive deformations toward a tetra-capped tetragonal antiprismatic geometry, which are probably related to the steric requirements of the interstitial carbide atom.
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