A Facile Synthesis and Crystallographic Analysis of Seven Trityl Phosphorus Compounds and Two Nickel(II) Phosphine Side-Products

Abstract  The syntheses and X-ray analyses of triphenylmethyl (trityl=Tr) phosphorus compounds are reported and the structural similarities, differences and ³¹P chemical shifts compared. A series of seven trityl-substituted phosphorus-containing compounds have been characterized by single crystal X-ray diffraction. Ph₃CPPh₂, 1, a bulky P(III) compound crystallizes in the triclinic space group , a = 7.5624(6) ?, b = 9.5470(8) ?, c = 16.9722(14) ?, α = 83.4720(10)°, β = 80.541(2)°, γ = 68.1580(10)°, the borane complex of 1, 2, Ph₃CPPh₂(BH₃) crystallizes as monoclinic colorless crystals, P2₁/c, a = 10.0972(12) ?, b = 9.6955(12) ?, c = 25.197(3) ?, β = 90.258(2)°. The analogous methyl substituted, 3, Ph₃CPMe₂(BH₃) is monoclinic, C₂/c, a = 15.628(3) ?, b = 12.770(3) ?, c = 18.406(4) ?, β = 103.968(3)°. Compounds 4–7 are trityl substituted P(V) compounds: Ph₃CP(Ph)(O)(OH), 4, crystallizes in the triclinic space group , a = 8.9847(18) ?, b = 9.7443(19) ?, c = 12.786(3) ?, α = 72.045(3)°, β = 72.031(3)°, γ = 78.769(3)°. Esterification of 4 affords TrCP(O)(Ph)OBn 5, space group, P2₁/c, a = 7.9196(5) ?, b = 31.701(2) ?, c = 19.8062(13) ?, β = 99.7750(10)°. A phosphonate diester was also characterized, Ph₃CP(O)(OEt)₂, 6, triclinic, , a = 7.9521(17) ?, b = 9.2205(19) ?, c = 14.471(3) ?, α = 85.906(4)°, β = 83.031(4)°, γ = 68.283(4)°. Treatment of the trityl H-phosphinic acid, Ph₃CPO₂H_2, with elemental selenium yields yellow crystals of 7, Ph₃CP(O)(OH)Se]_2, P2₁/c, a = 9.0603(4) ?, b = 22.3652(11) ?, c = 16.9134(7) ?, β = 107.035(2)°. In our efforts to isolate a nickel-phosphine complex, two Ni(II) complexes were crystallographically analyzed, Ni(OP(H)Ph₂)₆]₂BF₄ ⁻ 8 and 9. Complex 8 with an uncoordinated BF₄ ⁻ ion crystallizes as yellow orthorhombic crystals, Pbca, a = 18.8247(12) ?, b = 18.5518(12) ?, c = 21.0976(14) ?, while crystals of 9 are trigonal, , a = b = 13.1545(12) ?, c = 68.461(9) ?. Graphical Abstract  The syntheses and X-ray analyses of triphenylmethyl (trityl=Tr) phosphorus compounds are reported and the structural similarities, differences and ³¹P chemical shifts compared.