87183-51-5Relevant academic research and scientific papers
Reactions of transition-metal carbonyl anions with group 2B metal acceptors and the crystal structure of tetra-n-butylammonium tris(dicarbonyl(η5-cyclopentadienyl)iron)zincate
Petersen, Robert B.,Ragosta, Joseph M.,Whitwell II, George E.,Burlitch, James M.
, p. 3407 - 3415 (2008/10/08)
Complexes of the type M′(MLn)3- were prepared from the reaction of bis(transition-metal carbonyl)-group 2B metal acceptors, M′(MLn)2, where M′ is Zn, Cd, or Hg, with metal carbonyl anions, MLn- = FeCp(CO)2, WCp(CO)3, CrCp(CO)3, and Co(CO)4 (Cp = η5-C5H5), in dichloromethane or tetrahydrofuran. Among the crystalline complexes isolated was (n-Bu)4N+Zn[FeCp(CO)2]3-, which was characterized by single-crystal X-ray structure analysis. This compound crystallizes in space group P21/c with Z = 4 and monoclinic unit cell dimensions a = 9.8192 (3) A?, b = 21.813 (7) A?, c = 18.650 (5) A?, and β = 106.93 (2)°. This is the first tetrametal trigonal-planar zinc complex and has an average Zn-Fe distance of 2.541 A?. A partially refined X-ray structure of Me4N+Hg[Co(CO)4]3- revealed trigonal-planar coordination about mercury. By analysis of infrared spectroscopic data, approximate formation constants were determined for the complexes. For all complexes studied, the magnitudes of these constants were in the order Cd > Zn > Hg. The relative magnitudes of the formation constants were found to depend on M′, MLn, and solvent in a systematic way. Increasing the basicity of MLn in M′(MLn)2 decreases the magnitude of the complex formation for a given anion. Complex formation is decreased in solvents with high donor numbers. Evidence was also obtained for the equilibrium nature of complex formation.
