SOLID-STATE AND SOLUTION STRUCTURES OF [PNP][W(CO)5O2CCH3] AND [PNP][W(CO)4(PET3)O2CCH3] AND THE CO-LABILIZING ABILITY OF THE ACETATO LIGAND IN THESE ANIONIC DERIVATIVES Academic Article uri icon

abstract

  • The structures of [PNP] [W(CO)5O2CCH3] (1) and [PNP] [W(CO)4(PEt3)02CCH3] (2) have been determined by single-crystal X-ray investigations. Complex 1 crystallizes in the triclinic space group [formula omitted] with a = 10.544 (2) , b = 12.140 (1) , c = 17.095 (3) , = 104.28 (1), = 107.07 (1), = 91.43 (1), and Z = 2. The structure of 1 was refined to values of R1 = 0.035 and R2 = 0.045 for 54 atoms (all anisotropic) and 5528 reflections with I > 3<3(I). Complex 2 crystallizes in the monoclinic space group P21/c with a = 17.661 (5) , b = 32.502 (4) , c = 16.141 (4) , = 90.93 (4), and Z = 8. The discrepancy indices for 2 were R1 = 0.052 and R2 = 0.067 for 4542 reflections with I > 2(I). The two crystallographically independent formula units are structurally almost identical. The structure of the anion in 2 is best described as a distorted octahedron with a cisoid arrangement of the PEt3 and acetate ligands. The [formula omitted] anion in solution is shown to dissociate equatorial carbon monoxide, readily and stereoselectively, at ambient temperature. In contrast, the [formula omitted] anion under similar conditions is inert toward dissociative CO loss. In part this inertness in 2 might be ascribed to a tightening of the WC bonds in the ground-state molecule, i.e., WC (average) in 2 is ca. 0.10 shorter than WC (average) for the equatorial CO groups in 1. 1982, American Chemical Society. All rights reserved.

published proceedings

  • INORGANIC CHEMISTRY

author list (cited authors)

  • COTTON, F. A., DARENSBOURG, D. J., KOLTHAMMER, B., & KUDAROSKI, R.

citation count

  • 22

complete list of authors

  • COTTON, FA||DARENSBOURG, DJ||KOLTHAMMER, BWS||KUDAROSKI, R

publication date

  • April 1982