(DIPHENYLPHOSPHINE)GOLD(I), (DIPHENYLPHOSPHIDO)GOLD(I), AND (DIPHENYLPHOSPHINITO)GOLD(I) COMPLEXES - CRYSTAL-STRUCTURE OF [(PPH3)2N][AU(P(O)PH2)2]

[AuX(thtp)] (thtp = tetrahydrothiophene) reacts with PPh2H 1:1 to give [AuX(PPh2H)] (X = Cl (1) or Br (2)) or 1:2, in the presence of excess of NaClO4.H2O, to give [Au(PPh2H)2]ClO4 (3). A new high yield synthes is of the polymer [AuPPh2]n is reported by addition of concentrated aq ueous ammonia to the solution obtained from a 1:1 mixture of [AuCl(tht p)] and PPh2H in dichloromethane. Q[AuX2] reacts with [AuPPh2]n (1:1) to give Q[(AuX)2-(mu-PPh2)] (Q = (PPh3)2N = bis(triphenylphosphoranyli den)ammonium, X = Cl (4a), Br (5a), I (6); Q = Bu4N, X = Br (5b)). [Au Cl(thtp)] reacts with PPh2H and Proton Sponge (bdan = 1,8-bis(dimethyl amino)naphthalene) (2:1:1) to give [Hbdan][(AuCl)2(mu-PPh2)] (4b). [(P Ph3)2N][Au(acac)2] (Hacac = acetylacetone) reacts with PPh2H (i:2) to give, after air oxidation, [(PPh3)2N] [Au{P(O)Ph2}2] (7). The crystal structure of 7 was determined at 178-degrees-K (C60H50AuNO2P4, monocli nic, C2/c, a = 17.299(5), b = 12.487(4), c = 22.863(9) angstrom, beta = 91.47(3)-degrees; Z = 4). 7 shows exactly linear coordination at the gold atom, which lies on a center of symmetry. The P-Au bond length ( 2.324(2) angstrom) is significantly greater than in Bu4N[(AuBr)2(mu-PP h2)] and the P=O bond distance (1.499(4) angstrom) is similar to typic al values for phosphine oxides.