Metalmetal versus metalligand bonding in dimetal compounds with tridentate ligands Academic Article uri icon

abstract

  • Reaction of a 'VCl2·nTHF' solution, prepared by the reduction of VCl3(THF)3 with NaBEt3H in THF, and Lidpa (dpa = the anion of 2,2'-dipyridylamine) in a mixture of THF/toluene at reflux temperature yields the bioctahedral V2(dpa)4·THF (1) compound. A similar reaction performed in THF at 0°C gave [V2(dpa)3(μ-Cl)2Li2(THF)6][BEt3H] (2), in which a dpa ligand adopts a novel 'doubly-chelating/bridging' coordination mode. Compound 2 reacts with CH2Cl2 giving V2(dpa)3Cl2·2CH2Cl2 (3), a valence delocalized V(II)···V(6III) bioctahedral complex. In all three complexes, the formation of four additional metal-ligand bonds is favored over the formation of a V-V bond. The V···V separations are 3.038(2), 3.024(2) and 3.091(2) Å for 1-3, respectively. Crystal data are: compound 1, space group P2/n a = 13.102(2), b = 9.294(2), c = 16.510(4) Å, β = 98.98(2)°, V = 1985.7(6) Å3 and Z = 2; compound 2, space group I2/a, a = 19.4674(8), b = 14.390(1), c = 24.219(2) Å, β = 92.954(7)°, V = 6775.4(7) Å3 and Z = 2; compound 3, space group P21/c, a = 12.0853(8), b = 18.679(2), c = 16.709(2), β = 109.98(1)°, V = 3544.9(6) Å3 and Z = 4. (C) 2000 Elsevier Science S.A.

author list (cited authors)

  • Cotton*, F. A., Daniels, L. M., Murillo*, C. A., & Zhou, H.

citation count

  • 19

publication date

  • July 2000