Formation of a Bridging Phosphinidene Thorium Complex
Formation of a Bridging Phosphinidene Thorium Complex
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DOI：
10.1021/jacs.5b09826
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发表时间：
2015-12-02
影响因子：
15
通讯作者：
Walensky, Justin R.
中科院分区：
文献类型：
--
作者：
Behrle, Andrew C.;Castro, Ludovic;Walensky, Justin R.
报道了第一个钍膦烯配合物的合成和结构测定。2当量的（C5 Me 5）（2）Th（CH 3）（2）与H2 P的反应（2，4，6-（Pr 3C 6 H2）-Pr-i）在95 ℃产生[（C5 Me 5）（2）Th]（2）（mu（2）-P[（2，6-CH 2CHCH 3）2-4-（PrC 6 H2）-Pr-1]以及4当量的甲烷，2当量来自膦的去质子化和2当量来自2-和6-位上每个异丙基的一个甲基的C-H键活化。过渡态计算表明，该反应机理中的步骤是P-H，C-H，C-H，然后PH键活化形成膦叉。
The synthesis and structural determination of the first thorium phosphinidene complex are reported. The reaction of 2 equiv of (C5Me5)(2)Th(CH3)(2) with H2P(2,4,6-(Pr3C6H2)-Pr-i) at 95 C produces [(C5Me5)(2)Th](2)(mu(2)-P[(2,6-CH2CHCH3)2-4-(PrC6H2)-Pr-i] as well as 4 equiv of methane, 2 equiv from deprotonation of the phosphine and 2 equiv from C-H bond activation of one methyl group of each of the isopropyl groups at the 2- and 6-positions. Transition state calculations indicate that the steps in the mechanism are P-H, C-H, C-H, and then PH bond activation to form the phosphinidene.