A Trimetallic Gold Boride Complex with a Fluxional Gold-Boron Bond
A Trimetallic Gold Boride Complex with a Fluxional Gold-Boron Bond
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DOI：
10.1002/anie.200904774
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发表时间：
2009-01-01
影响因子：
16.6
通讯作者：
Oestreicher, Sebastian
中科院分区：
文献类型：
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作者：
Braunschweig, Holger;Brenner, Peter;Oestreicher, Sebastian
具有金-硼键的稳定化合物是罕见的，直到2006年，仅限于那些含有超配位硼配体的化合物，例如，多金属单硼团簇[1]和配合物，其中{LAu+}片段正式桥接碳硼烷团簇的顶端硼原子和另一个金属原子事实证明，将低配位硼与金连接起来是一项具有挑战性的任务，但最近的研究表明，这只不过是一个合成障碍。构建过渡金属-硼键的传统方法（基于B+/MÀ极性）[3]被发现是不合适的：AuI似乎缺乏足够的还原强度或亲核性来扰乱硼卤化键或给予非桥接的刘易斯酸性硼烷。由于硼基亲核试剂的缺失，直到最近，基于相反极性（BÀ/M+）的合成策略才被认为是不可想象的在过去的三年中，这两种策略都取得了成功，并发现了两种新的硼金配位模式，即硼金配合物(Au！B)和硼基金配合物(Au
Stable compounds featuring gold–boron bonds are rare, and until 2006, were limited to those containing hypercoordinate boron ligands, for example, polymetallic monoboron clusters [1] and complexes in which a {LAu+} fragment formally bridges an apical boron atom of a carborane cluster and another metal atom.[2] Linking low-coordinate boron to gold has proved a challenging task, but this has recently been shown to reflect little more than a synthetic roadblock. Traditional methods for constructing transition-metal–boron bonds (based on B+/MÀ polarity)[3] were found to be unsuitable: AuI appears to lack sufficient reducing strength or nucleophilicity to perturb boron–halide bonds or to donate to an nonbridging Lewis acidic borane. Synthetic strategies based on the opposite polarity (BÀ/M+) were unthinkable until very recently, because of the absence of boron-based nucleophiles.[4] In the last three years, success has been found with both of these strategies, and two new boron–gold coordination modes have been discovered, namely the borane gold complexes (Au! B), and the boryl gold complexes (Au