A study of a variety of O,O-alkylene dithiophosphate derivatives of triphenyl-and diphenylgermane. Crystal structures of and

Abstract

The O,O-alkylene dithiophosphate derivatives of triphenyl- and diphenylgermane, [Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text] [Formula: see text] and [Formula: see text] have been prepared and characterized by infrared, Raman, and 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, and, in three cases, X-ray crystallography. [Formula: see text] 1, crystallizes as monoclinic in the space group P21/a (No. 14) with the cell parameters a = 12.868(5) Å, b = 11.354(4) Å, c = 17.207(4) Å, β = 95.42(2)°, V = 2502(1) Å3, Z = 4, R = 0.0640, and Rw = 0.0585. [Formula: see text] 2, crystallizes as orthorhombic in the space group Pbca (No. 61) with the cell parameters a = 23.007(4) Å, b = 16.840(4) Å, c = 12.068(3) Å, V = 4657(3) Å3, Z = 8, R = 0.0502, and Rw = 0.0329. [Formula: see text] 3, crystallizes as monoclinic in the space group C2/c (No. 15) with the cell parameters a = 35.48(2) Å, b = 9.275(5) Å, c = 20.78(1) Å, β = 120.93(3)° V = 5866(5) Å3, Z = 8, R = 0.0674, and Rw = 0.0562. As with their methylgermanium analogues, the environment about germanium is essentially that of a distorted tetrahedron, with the terminal sulfur atoms oriented towards germanium rather than away from it, in contrast with analogous noncyclic dithiophosphatogermanes. The substituents on the atoms in both the five- and six-membered rings maintain their nonequivalence in solution, in contrast with tin analogues. Keywords: structure, germanium, diphenyl, triphenyl, cyclic dithiophosphates