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The molecular structures of two carbaboranes, closo-2,3-C(2)B(9)H(11) and nido-2,9-C(2)B(9)H(13), were determined experimentally for the first time using gas-phase electron diffraction (GED). For closo-2,3-C(2)B(9)H(11), a model with C(2)(v)() symmetry was refined to give C-B bond distances ranging 158.3-167.0 pm and B-B distances ranging 177.4-200.0 pm. The structure of nido-2,9-C(2)B(9)H(13) was refined using a model with C(s)() symmetry to give C-B bond lengths ranging 160.3-171.9 pm and B-B lengths ranging 173.0-196.1 pm. Ab initio computations (up to MP2/6-311+G) were also carried out on these and the related nido-7,8-C(2)B(9)H(13), which was not sufficiently stable to allow determination of its molecular structure by GED.

The structure of the title compound, [Ta2O(C2B9H11)2(C4H9N2)4]*0.5CH2Cl2, contains two (C2B9H11)Ta[NC(Me)NMe2]2 units bridged by a nearly linear [Ta-O-Ta 163.4 (4) degrees ] mu-oxo ligand. The dichloromethane molecule lies on a twofold axis.

In ethanol the charge-compensated molecule exo-nido-ruthenacarborane [5,6,10-{RuCl(PPh(3))(2)}-5,6,10-&mgr;-(H)(3)-10-H-7,8-C(2)B(9)H(8)] reacts with KOH to afford the anionic closo-complex [RuH(PPh(3))(2)(eta(5)-7,8-C(2)B(9)H(11))](-) isolated as its K(+) (2a) or [K(18-crown-6)](+) (2b) salt. Treatment of 2a with CO gives [Ru(CO)(PPh(3))(2)(eta(5)-7,8-C(2)B(9)H(11))] (3a) in high yield; its structure was determined by X-ray crystallography. In contrast 2b reacts with CO to yield the salt [K(18-crown-6)][RuH(CO)(PPh(3))(eta(5)-7,8-C(2)B(9)H(11))] (2d). Reaction of 2b with [RuCl(2)(PPh(3))(3)] affords [Ru(2)(&mgr;-H)(H)(PPh(3))(4)(eta(5)-7,8-C(2)B(9)H(11))] (5), which with CO produces [Ru(2)(&mgr;-H)(&mgr;-sigma: eta(5)-7,8-C(2)B(9)H(10))(CO)(4)(PPh(3))(2)] (6), the structure of which was established by X-ray diffraction. The molecule has a metal-metal bond bridged on one side by a hydrido ligand and on the other by a nido-7,8-C(2)B(9)H(10) fragment. The latter is eta(5)-coordinated to a ruthenium atom ligated by a PPh(3) and a CO ligand and is also sigma-bonded to the second ruthenium which carries three CO molecules and a PPh(3) group. The sigma bond utilizes a boron lying in an alpha site with respect to the carbons in the ring coordinated to the Ru(CO)(PPh(3)) moiety. Reactions between 2b or 2d and [CuCl(PPh(3))(3)] and [AuCl(PPh(3))], respectively, afford the bimetal complexes [RuM(&mgr;-H)(L)(PPh(3))(2)(eta(5)-7,8-C(2)B(9)H(11))] [M = Cu, L = PPh(3) (7a), L = CO (7b); M = Au, L = PPh(3) (8a), L = CO (8b)]. X-ray diffraction studies are reported for 7a and 8a, revealing in the case of the former a structure in which an exopolyhedral B-Hright harpoon-up Cu bond supplements the Ru(&mgr;-H)Cu interaction.