Gold(I) phosphido complexes: synthesis, structure, and reactivity

Diana M Stefanescu; Holming F Yuen; David S Glueck; James A Golen; Lev N Zakharov; Christopher D Incarvito; Arnold L Rheingold

doi:10.1021/ic035006e

Gold(I) phosphido complexes: synthesis, structure, and reactivity

Inorg Chem. 2003 Dec 29;42(26):8891-901. doi: 10.1021/ic035006e.

Authors

Diana M Stefanescu¹, Holming F Yuen, David S Glueck, James A Golen, Lev N Zakharov, Christopher D Incarvito, Arnold L Rheingold

Affiliation

¹ 6128 Burke Laboratory, Department of Chemistry and Dartmouth Molecular Materials Group, Dartmouth College, Hanover, New Hampshire 03755, USA.

PMID: 14686872
DOI: 10.1021/ic035006e

Abstract

Deprotonation of the phosphine complexes Au(PHR(2))Cl with aqueous ammonia gave the gold(I) phosphido complexes [Au(PR(2))](n)() (PR(2) = PMes(2) (1), PCy(2) (2), P(t-Bu)(2) (3), PIs(2) (4), PPhMes (5), PHMes (6); Mes = 2,4,6-Me(3)C(6)H(2), Is = 2,4,6-(i-Pr)(3)C(6)H(2), Mes = 2,4,6-(t-Bu)(3)C(6)H(2), Cy = cyclo-C(6)H(11)). (31)P 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[AuCl(2)] gave PPN[(AuCl)(2)(micro-PR(2))] (9-12, PPN = (PPh(3))(2)N(+)). Treatment of 3 with the reagents HI, I(2), ArSH, LiP(t-Bu)(2), and [PH(2)(t-Bu)(2)]BF(4) gave respectively Au(PH(t-Bu)(2))(I) (14), Au(PI(t-Bu)(2))(I) (15), Au(PH(t-Bu)(2))(SAr) (16, Ar = p-t-BuC(6)H(4)), Li[Au(P(t-Bu)(2))(2)] (17), and [Au(PH(t-Bu)(2))(2)]BF(4) (19).