Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes
作者:Nana Kim、Ross A. Widenhoefer
DOI:10.1039/c9sc01574d
日期:——
Cationic gold vinyl carbene/allylic cation complexes of the form (E)-[(L)AuC(H)C(H)CAr2]+ OTf− L = IPr, Ar = Ph [(E)-5a], L = IPr, Ar = 4-C6H4OMe [(E)-5b], L = P(t-Bu)2o-biphenyl, Ar = 4-C6H4OMe [(E)-5c]} were generated in solution via Lewis acid-mediated ionization of the corresponding gold (γ-methoxy)vinyl complexes (E)-(L)AuC(H)C(H)C(OMe)Ar2 at or below −95 °C. Complexes (E)-5b and (E)-5c were
( E )-[(L)AuC(H)C(H)CAr 2 ] + OTf - L = IPr, Ar = Ph [( E )- 5a ], L形式的阳离子金乙烯基卡宾/烯丙基阳离子配合物= IPr, Ar = 4-C 6 H 4 OMe [( E )- 5b ], L = P( t -Bu) 2邻联苯, Ar = 4-C 6 H 4 OMe [( E )- 5c ]}通过路易斯酸介导的相应金 (γ-甲氧基) 乙烯基络合物 ( E )-(L)AuC(H)C(H)C(OMe)Ar 2的电离在溶液中产生-95 °C 或以下。配合物 ( E )- 5b和 ( E )- 5c在溶液中使用多核 NMR 光谱进行了充分表征,这确定了金烯丙基阳离子共振结构的主要贡献以及正电荷在 γ-茴香环中的显着分布。配合物 ( E )- 5b在 -95 °C 下与仅在乙烯基卡宾部分的 C1 位上的中性双电子、氢化物和氧原子