FORMATION OF PPH4[WOCL4 BULLET THF] AND PPH4CL BULLET 4AS4S3 FROM W(CO)6 AND PPH4[AS2SCL5] AND THEIR CRYSTAL-STRUCTURES

When W(CO)6 and PPh4[As2SCl5] are irradiated with UV light in tetrahydrofuran, PPh4[WOCl4 . THF], PPh4Cl . 4As4S3 and PPh4[Cl2H] are obtained. X-ray crystal structure determinations were performed. PPh4[WoCl4 . THF], monoclinic, space group P2(1)/c, Z = 4, a = 1 207.5(2), b = 1 003.7(2), c = 2 642.0(5) pm, beta = 114.71(1)-degrees, R = 0.049% for 2 824 reflexions; PPh4+ and [WOCl4 . THF]- ions are present, the WOCl4 group having the shape of a tetragonal pyramid with a short W = O bond (169 pm) and the THF molecule being weakly associated (W-O 236 pm). PPh4Cl . 4AsS3, tetragonal, I4(1)/a, Z = 4, a = 1 742.3(3), c = 1 664.5(4) pm, R = 0.066% for 1 350 reflexions; it consists of separate PPh4+ and Cl- ions and As4S3 molecules.