Terminal Coordination of a Gallium(I) Species to a Transition Metal. Syntheses and Crystal Structures of Ru{GaCl(THF)(2)}{GaCl(2)(THF)}(2)(CO)(3).0.5THF and Ru(2){GaCl(2)(THF)}(2)(CO)(8).

The reaction of Ru(3)(CO)(12) with Ga(2)Cl(4) in the presence of gallium metal in refluxing toluene, followed by crystallization from tetrahydrofuran, produces Ru{GaCl(THF)(2)}{GaCl(2)(THF)}(2)(CO)(3).0.5 THF (1) and Ru(2){GaCl(2)(THF)}(2)(CO)(8) (2) (THF = tetrahydrofuran). The ruthenium atom in 1 has an approximately octahedral coordination environment, with meridinal arrangements of carbonyl ligands and gallium atoms. The GaCl(THF)(2) group is in a position trans to one of the GaCl(2)(THF) groups. The crystal structure of 2 consists of a linear arrangement of metal atoms in which two GaCl(2)(THF) groups are in axial positions with respect to the metal-metal bond of an Ru(2)(CO)(8) unit. Crystal data for 1: monoclinic space group P2(1)/c (No. 14), a = 17.367(3) Å, b = 12.054(2) Å, c = 16.049(3) Å, beta = 95.18(1) degrees, Z = 4, R = 0.0527, R(w) = 0.0718. Crystal data for 2: monoclinic space group P2(1)/c (No. 14), a = 11.980(1) Å, b = 6.944(1) Å, c = 16.097(3) Å, beta = 96.81(1) degrees, Z = 2, R = 0.0300, R(w) = 0.0510. The title complexes are the first compounds to contain ruthenium-gallium bonds, and compound 1 is the second structurally-characterized example of a complex in which a gallium(I) species is terminally coordinated to a transition metal.