111920-15-1Relevant articles and documents
Synthesis and characterization of phosphinosilylalanes from [(CH3)3Si]3Al. Crystal and molecular structure determinations of {[(CH3)3Si]2AlP(C6H 5)2}2, {[(CH3)3Si]2AlP(C6H 5)[Si(CH ...
Janik, Jerzy F.,Duesler, Eileen N.,McNamara, William F.,Westerhausen, Matthius,Paine, Robert T.
, p. 506 - 514 (2008/10/08)
Full title: Synthesis and characterization of phosphinosilylalanes from [(CH3)3Si]3Al. Crystal and molecular structure determinations of {[(CH3)3Si]2AlP(C6H 5)2}2, {[(CH3)3Si]2AlP(C6H 5)[Si(CH3)3]}2, {[(CH3)3Si]2AlP(H)(c-C6H 11)}3, and [{[(CH3)3Si]2N}(C6H 5)P]2. The reactions of [(CH3)3Si]3Al·O(C2H 5)2 with phosphines (C6H5)2PCl, PCl3, {[(CH3)3Si]2N}(C6H5)PCl, (C6H5)2PH, [(CH3)3Si](C6H5)PH, (C6H5){[(CH3)3Si]2N}PH, (C-C6H11)PH2, and PH3 were surveyed. Reactions of the chlorophosphines led to formation of di- or polyphosphines, and the molecular structure of [{[(C-H3)3Si]2N}(C6H 5)P]2 was determined by single-crystal X-ray diffraction analysis. The compound crystallized in the tetragonal space group I41/a with a = 24.379 (9) A?, c = 10.778 (3) A?, Z = 8, V = 6405.8(4) A?, and ρcalcd = 1.11 g cm-3. Least-squares refinement gave RF = 6.3% and RwF = 5.3% on 1613 reflections with F ≥ 4σ(F). The diphosphine has C1 symmetry, and each phosphorus atom has pseudotetrahedral geometry: P-P = 2.270 (3) A? and P-N = 1.724 (4) A?. The remaining phosphines form Lewis acid-base complexes with [(CH3)3Si]3Al and/or undergo elimination/condensation chemistry resulting in production of phosphinoalane ring compounds or polymers. The molecular structures of three additional compounds have been determined by single-crystal X-ray diffraction analysis. The compound {[(CH3)3Si]2AlP(C6H 5)2}2 crystallized in the triclinic space group P1 (No. 2) with a = 10.989 (3) A?, 6 = 20.576 (5) A?, c = 21.000 (5) A?, α = 101.52 (2)°, β = 102.17 (2)°, γ = 100.86 (2)°, Z = 4, V = 4414 (2) A?3, and ρcalcd = 1.08 g cm-3. Least-squares refinement gave RF = 11.3% and RwF = 9.6% on 7466 reflections with F > 3σ(F). The compound {[(CH3)3Si]2AlP(C6H 5)[Si(CH3)3]}2 crystallized in the monoclinic space group P21/n with a = 11.360 (8) A?, b = 12.215 (7) A?, c = 16.673 (12) A?, β = 102.13 (5)°, Z = 2, V = 2261 (2) A?3, and ρcalcd = 1.04 g cm-3. Least-squares refinement gave RF = 9.9% and RwF = 7.7% on 2718 reflections with F ≥ 3σ(F). The compound {[(CH3)3Si]2AlP(H)(c-C6H 11)}3 crystallized in the triclinic space group P1 (No. 2) with a = 12.564 (2) A?, b = 12.935 (3) A?, c = 19.149 (4) A?, α = 83.66 (2)°, β = 88.64 (2)°, γ = 66.65 (1)°, Z = 2, V = 2839 (1) A?3, and ρcalcd = 1.01 g cm-3. Least-squares refinement gave RF = 11.3% and RwF = 8.6% and 5213 reflections with F ≥ 3σ(F). The first two compounds contain planar four-membered (ALP)2 rings with C1 symmetry and average Al-P distances of 2.455 and 2.466 A?, respectively. The third compound forms a six-membered skew-boat cyclohexane-like (AlP)3 ring with an E, E, A conformation and an average Al-P distance of 2.444 A?. Pyrolysis of a polymeric product obtained from reactions involving PH3 and [(C-H3)3Si]3Al·O(C2H 5)2 resulted in formation of aluminum phosphide, AlP.
