USE OF ORGANOINDIUM HYDRIDES FOR THE PREPARATION OF ORGANOINDIUM PHOSPHIDES - SYNTHESIS AND MOLECULAR-STRUCTURE OF [(ME3CCH2)2INP(T-BU)2]2

The indium phosphide [(Me3CCH2)2InP(t-Bu)2]2 has been prepared from K[In(CH2CMe3)3H] and ClP(t-Bu)2 in pentane. When In(CH2CMe3)3 and HP(t-Bu)2 were present in a 1:1 mol ratio, heating to 105-115-degrees-C for 5 days was required, whereas when In(CH2CMe3)3 and HP(t-Bu)2 were in a 5:1 mol ratio in pentane solution, the desired indium product formed in 6 days at room temperature. Excess phosphine, In(CH2CMe3)3, and HP(t-Bu)2 in a 1:5 mol ratio in pentane, significantly retarded the rate of formation of [(Me3CCH2)2InP(t-Bu)2]2. Thermal decomposition of [(Me3CCH2)2InP(t-Bu)2]2 to form InP occurred at 245-degrees-C in 1 h. The compound [(Me3CCH2)2InP(t-Bu)2]2 crystallizes in the centrosymmetric orthorhombic space group Pbcn (No. 60) with a = 11.742(3) angstrom, b = 20.194(6) angstrom, c = 17.909(4) angstrom, V = 4246(2) angstrom3, and Z = 4. The structure was solved and refined to R = 6.68% and R(w) = 6.24% for all 4920 independent reflections and R = 2.76% and R(w) = 3.47% for those 2525 reflections with \F(o)\ > 6.0sigma(\F(o)\). The molecule lies on a 2-fold axis which passes through the two indium atoms and requires that the In2P2 core be strictly planar.