Use of organoindium hydrides for the preparation of organoindium phosphides. Synthesis and molecular structure of [(Me3CCH2)2InP(t-Bu)2]2

Article abstract of DOI:10.1021/om00034a035

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°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°C in 1 h. The compound [(Me₃-CCH₂)₂InP(t-Bu)₂]₂ crystallizes in the centrosymmetric orthorhombic space group Pbcn (No. 60) with a = 11.742(3) A?, b = 20.194(6) A?, c = 17.909(4) A?, V = 4246(2) A?³, 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| > 6.0σ(|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.