Facile Buchwald-Hartwig coupling of sterically encumbered substrates effected by PNP ligands.

The diphosphinoamine ligands [(Ph2P)2N(Ar); 1 (Ar = C6H5), 2 (Ar = 2,6-iPr2C6H3)] were effectively utilized in Buchwald-Hartwig coupling of a range of sterically demanding substrates. The reaction was carried out using conventional and microwave routes and the latter reduces the reaction time from 3 d to 15-30 min. A broad substrate scope was achieved in this protocol and most of the coupling products are isolated on a mutligram scale.

Stepwise isolation of an unprecedented silylene supported dinuclear gold(i) cation with aurophilic interaction.

The silylene (PhC(NtBu)2SiN(PPh2)(2,6-iPr2-C6H3)) (2) was prepared from the previously reported (PhC(NtBu)2SiCl) salt elimination method. The reaction of 2 with AuCl(SMe2) afforded [(PhC(NtBu)2SiN(PPh2)(2,6-iPr2-C6H3))AuCl] (3). Note here that only Si(ii) is coordinated to Au(i), while P(iii) remains uncoordinated.

Synthesis, Characterization, and Luminescence Studies of Gold(I) Complexes with PNP- and PNB-Based Ligand Systems.

The synthesis, X-ray crystal structures, and spectroscopic studies of a series of PPh2N(2,6-iPr2C6H3)PPh2 (PNP) and PPh2N(2,6-iPr2C6H3)BCy2 (PNB; Cy = cyclohexyl) based gold(I) complexes are presented herein. The gold(I) chloride complexes 2 and 6 were treated with AgSbF6 to yield the corresponding dimeric dinuclear Au(I) cation (3) and dimeric mononuclear Au(I) cation (7) with PNP and PNB systems, respectively. The molecular structure of 3 revealed the presence of a strong intramolecular aurophilic interaction with a Au···Au bond distance of 2.