Bis(diphenylphosphino)methane complexes of rhodium(III) halides as synthons for dinuclear rhodium(III) complexes Academic Article uri icon

abstract

  • Several rhodium(III) complexes have been synthesized by the reaction of dirhodium tetraacetate, Rh2(O2CCH3)4, with bis(diphenylphosphino)methane (dppm), in the presence of trimethylsilyl halides. Octahedral complexes of formula RhCl3(dppm)(CH3CN) (1) and RhI3(dppm)(CH3CN) (2) have been isolated as minor products in the reaction between Rh2(O2CCH3)4, dppm and Me3SiCl or Me3SiI, respectively. In addition, the tri-n-butylphosphine complex RhCl3(dppm)(P-n-Bu3) (3) has also been prepared either by treatment of 1 with P-n-Bu3 or from the reaction of Rh2Cl6(P-n-Bu3)4 with dppm. Dimerization occurs upon heating 3 at 150 °C in vacuo for 2 h to form the Rh(II) complex Rh2Cl4(dppm)2, which we have previously reported. X-ray crystallographic characterization of 1, 2 and 3 gave the following: for 1: space group I4̄, a=19.090(4), c=15.100(3) Å, V=5503(1) Å-3, Z=8; for 2: space group Cc, a=11.897(2), b=17.110(3), c=15.246(1)Å, β=106.04(9)°, V=2983(1)-3, Z=4; for 3: space group P212121, a=15.914(4), b=19.819(6), c=12.207(3) Å, V=3850(2) Å3, Z=4. © 1991.

author list (cited authors)

  • Cotton, F. A., Dunbar, K. R., Eagle, C. T., Falvello, L. R., Seong-Joo, K., Price, A. C., & Verbruggen, M. G.

citation count

  • 8

publication date

  • June 1991