Abstract
The dimeric tantalum(III) phosphine complex Ta/sub 2/Cl/sub 6/(PMe/sub 3/)/sub 4/ (1) has been prepared from the reaction of tantalum pentachloride, trimethylphosphine, and sodium amalgam in toluene. The compound crystallizes in the noncentrosymmetric orthorhombic space group P2/sub 1/2/sub 1/2/sub 1/ with a = 11,681 (3) angstroms, b = 11.834 (3) angstroms, C = 20.257 (7) angstroms, V = 2800.18 angstroms/sup 3/, and rho(calcd) = 2.085 g cm/sup -3/ for mol wt 878.9 and Z = 4. The structure refined to R/sub F/ = 0.037 and R/sub wF/ = 0.035. 1 is a distorted edge-sharing bioctahedral complex with axial phosphines on one tantalum and equatorial phosphines on the second. Direct P-P coupling is observed across the dimer with J/sub PP'/ = 2.46 Hz. The metal-metal bond length in 1 is 2.721 (1) angstroms, and the formal metal-metal bond order in this d/sup 2/-d/sup 2/ dimer is 2.
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