作者:Ajay Venugopal、Manik Kumer Ghosh、Hannes Jürgens、Karl W. Törnroos、Ole Swang、Mats Tilset、Richard H. Heyn
DOI:10.1021/om100038f
日期:2010.5.24
The reaction between [Me,AuCl], and the lithium salt of a beta-diketimine, [HCC(Me)N(C(6)H(3)-2, 6-Me(2))}(2)Li], yields the neutral Au(III) compound [HCC(Me)N(C(6)H(3)-2,6-Me(2))}(2)AuMe(2)] (1). Compound 1 reacts with I equiv of triflic acid (HOTf) at 78 C to provide the cationic Au(III) compound [H(2)CC(Me)N(C(6)H(3)-2,6-Me(2))}(2)AuMe(2)][OTf] (2). Treatment of I with 2 equiv of HOTf results in the displacement of Me(2)AuOTf and formation of the beta-diketiminato triflate salt [HCC(MONH(C(6)H(3)-2,6-Me)}(2)][OTf] (3). Compound I reacts with I(2) to yield the cation [HC(I)-C(Me)N(C(6)H(3)-2,6-Me(2))}(2)AuMe(2)](+), which is isolated as the triflate salt [HC(I)C(Me)N(C(6)H(3)-2,6-Me(2))}(2)AuMe(2)][OTf] (4). The reaction of 1 with (PPh(3))AuCl in the presence of AgOTf provides [HC(AuPPh(3))C(Me)N(C(6)H(3)-2,6-Me(2))}(2)AuMe(2)][OTf] (5). Molecular structures of 1, 4, and 5 were elucidated by single-crystal ti-ray diffraction experiments; that of 4 was additionally confirmed by quantum-chemical calculations. The reactivity experiments indicate that the methine carbon in the beta-diketiminato unit of I is the exclusive site of electrophilic attack, while the Au C bonds are not perturbed.