Solid-State and Dynamic Solution Behavior of a Cationic, Two-Coordinate Gold(I) π-Allene Complex
Solid-State and Dynamic Solution Behavior of a Cationic, Two-Coordinate Gold(I) π-Allene Complex
复制标题
DOI：
10.1021/om100688t
复制
发表时间：
2010-10-11
期刊：
影响因子：
2.8
通讯作者：
Widenhoefer, Ross A.
中科院分区：
文献类型：
--
作者：
Brown, Timothy J.;Sugie, Atsushi;Widenhoefer, Ross A.
从3-甲基-1，2-丁二烯与[P（t-Bu）（2）邻-联苯]AuCl和AgSbF 6的混合物的反应中以98%的产率分离出阳离子金π-联烯配合物{[P（t-Bu）（2）邻-联苯]Au[eta（2）-H2 C-C-C（CH 3）（2）]}（+）SbF 6-，并通过X射线晶体学和变温核磁共振光谱进行表征。这些研究揭示了在固态和溶液中金与丙二烯的较少取代的C-C键的优先结合，并且还揭示了与丙二烯配体经由η（1）-C2丙二烯中间体或过渡态的π-面交换一致的流动行为。
The cationic gold pi-allene complex {[P(t-Bu)(2)o-biphenyl]Au[eta(2)-H2C-C-C(CH3)(2)]}(+) SbF6- was isolated in 98% yield from reaction of 3-methyl-1,2-butadiene with a mixture of [P(t-Bu)(2)o-biphenyl]AuCl and AgSbF6 and was characterized by X-ray crystallography and variable-temperature NMR spectroscopy. These studies revealed preferential binding of gold to the less substituted C-C bond of the allene in both the solid state and solution and also revealed fluxional behavior consistent with pi-face exchange of the allene ligand via an eta(1)-C2 allene intermediate or transition state.