Deprotonation of the phosphine complexes Au(PHR2)Cl with aqueous ammonia gave the gold(l) phosphido complexes [Au(PR2)](n) (PR2 = PMeS2 (1), PCy2 (2), P(t-Bu)(2) (3), Pls(2) (4), PPhMes (5), PHMes* (6); Mes = 2,4,6-Me3C6H2, Is = 2,4,6-(i-Pr)(3)C6H2, Mes* = 2,4,6-(t-Bu)(3)C6H2, Cy = cyclo-C6H11). P-31 NMR spectroscopy showed that these complexes exist in solution as mixtures, presumably oligomeric rings of different sizes. X-ray crystallographic structure determinations on single oligomers of 1-4 revealed rings of varying size (n = 4, 6, 6, and 3, respectively) and conformation. Reactions of 1-3 and 5 with PPN[AuCl2] gave PPN[(AuCl)(2)(mu-PR2)] (9-12, PPN = (PPh3)(2)N+). Treatment of 3 with the reagents HI, I-2, ArSH, LiP(t-Bu)(2), and [PH2(t-Bu)(2)]BF4 gave respectively Au(PH(t-Bu)(2))(1) (14), Au(PI(t-Bu)(2)(I) (15), Au(PH(t-Bu)(2))(SAr) (16, Ar = p-t-BuC6H4), Li[Au(P(t-Bu)(2))(2)] (17), and [Au(PH(t-Bu)(2))(2)]-BF4 (19).