REACTIONS OF METHYLPHOSPHINES (CH3)NPCL3-N(N = 1-3) WITH METHYLCHLOROSULFANE AND CRYSTAL-STRUCTURES OF (CH3)3PSCH3+I- AND CH3P(SCH3)CL2+SBCL6-

The new thiophosphonium compounds (CH3)nP(SCH3)Cl3-n+Cl- (n = 1-3) are prepared by reaction of methylphosphines (CH3)nPCl3-n (n = 1-3) with CH3SCl in CH2Cl2. CH3P(SCH3)Cl2+Cl- reacts with AlCl3 or SbCl5 to give the tetrachloroaluminate and the hexachloroantimonate, respectively. Likewise (CH3)2P(SCH3)Cl+SbCl6- is formed from the chloride and SbCl5. All compounds are characterized by vibrational and NMR spectroscopy. CH3P(SCH3)Cl2+SbCl6- crystallizes in the monoclinic space group P2(1)/n with a = 929(2), b = 1095(2), c = 1436(3) pm, beta = 93,1(2)-degrees and Z = 4. (CH3)3PSCH3+I- crystallizes in the same space group with a = 705,2(4), b = 1360,6(8), c = 941,8(4) pm, beta = 93,85(4)degrees and Z = 4.