METAL DONOR-]METAL ACCEPTOR COMPLEXES - FE(CO)42- HFE(CO)4-, AND TRANS-HFE(CO)3P(OME)3- AS ANIONIC LIGANDS TO CR(CO)50, W(CO)50 Academic Article uri icon

abstract

  • A series of heterobimetallic carbonyl anions have been synthesized and structurally characterized as their bis-(triphenylphosphine)iminium salts. Compound 1, crystallizes in space group P1 (Z = 2): a = 14.099 (5) A, b = 11.601 (5) A, c = 14.148 (5) A, a = 95.53 (3),= 118.23 (3), = 92.39 (3), 2026 (3) A3; Rw = 0.061 for 3637 unique reflections measured >3(I). Compound 2, PPN+HFeW(CO)8P(OMe)3- crystallizes in space group P21/N (Z = 4): a = 12.200 (2) A, b = 12.461 (2) c =32.032 (4) A, a = 90.00, = 96.40 (1), y = 90.00, V = 4838 (2) A3; Rw = 0.069 for 1769 unique reflections measured >3(I). Compound 3, PPN+HFeCr(CO)9-, crystallizes in space group (Z =2): a = 11.717 (2) A, b = 14.095 (3) A, c = 14.283 (2) a = 92.18 (2), = 117.51 (1), y = 95.78 (2), V = 2072 (1) A3; = 0.053 for 1321 unique reflections measured >3(I). Finally, compound 4, (PPN+)2FeCr(CO)92-, crystallizes in space group PI (Z = 2): a = 13.882 (2) A, b = 22.825 (4) A, c = 13.067 (2) A, a =96.07 (1), = 117.57 (1), y = 87.27 (1), V = 3650 (2) A3; Rw =0.060 for 3905 unique reflections measured >3(I). The structural features common to all complexes are all terminal CO groups and a Fe-M (M = Cr, W) bond. This bond is viewed as a Fe: M donor-acceptor complex in which Fe- donates to an electrophilic group 6 metal pentacarbonyl moiety. In the series, the Fe-M bond distance ranges from 2.941 (2) A for 4 to 2.997 (2) A for 1. The small bond distance change of 0.015 A on going from the dianion 4 to the protonated form 3 and the appropriate angle deformations as well as the identical M-CO arrangement of the Ph3PAuFeW(CO)9- anion suggest the hydride to be terminal and located solely on Fe. Various spectral (IR, 13C NMR) and chemical characterizations are also reported. 1986, American Chemical Society. All rights reserved.

published proceedings

  • JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

author list (cited authors)

  • ARNDT, L. W., DARENSBOURG, M. Y., DELORD, T., & BANCROFT, B. T.

citation count

  • 34

complete list of authors

  • ARNDT, LW||DARENSBOURG, MY||DELORD, T||BANCROFT, BT

publication date

  • May 1986