CARBON-DIOXIDE INSERTION AND DEINSERTION PROCESSES INVOLVING METAL-CARBON BONDS - SOLID-STATE STRUCTURE OF [PPN][W(CO)5CH2CN]

The synthesis and X-ray structure of [PPN][W(CO)5CH2CN] are reported. The complex crystallizes in the triclinic space group P1BAR, with unit cell dimensions a = 12.771 (4) angstrom, b = 13.410 (4) angstrom, c = 13.850 (5) angstrom, alpha 54.41 (3)-degrees, beta = 68.65 (3)-degrees, gamma = 83.98 (3)-degrees, V = 1988 (2) angstrom 3, Z = 2, and R(F) = 4.13%. The W-CH2CN bond distance was found to be 2.330 (8) angstrom, a value quite similar to that found in the W-CH3 analogue. Unlike W(CO)5CH3-, the W(CO)5CH2CN- anion does not react with carbon dioxide even under very high pressure. Furthermore, the cyanoacetate derivative, W(CO)5O2CCH2CN-, prepared from cyanoacetate and W(CO)5THF, does not undergo decarboxylation either in solution or in the solid state. On the other hand, the W(CO)5O2CCH2CN- complex is a catalyst for the homogeneous decarboxylation of cyanoacetic acid.