Synthesis and Characterization of 5-Coordinate Tungsten Hydride Anions: [( t Bu 3 SiNH)( t Bu 3 SiN=) 2 HWR]M
Synthesis and Characterization of 5-Coordinate Tungsten Hydride Anions: [( t Bu 3 SiNH)( t Bu 3 SiN=) 2 HWR]M
复制标题
5配位氢化钨阴离子的合成与表征：[( t Bu 3 SiNH)( t Bu 3 SiN=) 2 HWR]M
DOI：
10.1002/ijch.201700042
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发表时间：
2017
影响因子：
3.2
通讯作者：
MacMillan, Samantha N.
中科院分区：
文献类型：
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作者：
Schafer, II, Daniel F.;Wolczanski, Peter T.;Lobkovsky, Emil B.;MacMillan, Samantha N.
(TBu3SiNH)(tBu3SiN=)2WH(1-H)与小分子烷基阴离子(Rm)反应得到了钨的烷基氢化物阴离子[(TBu3SiNH)(tBu3SiN=)2HWR]M(3-(R)M：R=CH3，M=Li；R=NBU，M=Li；R=nePe，M=Li；R=CH2Ph(Bn)，M=K(两个异构体)；R=CCH，M=Na；R=CH=CH2(Vy)，M=Li)。饱和烷基阴离子3-(R)M(3-(R)M：R=CH3，M=Li；R=NBU，M=Li；R=nePe，M=Li；R=CH2Ph(Bn)，M=K)通过表观1，2-RH消除反应降解生成[(tBu3SiN=)3WH]M(2-HM)，但乙炔(3-(C2H)Na)和乙烯基(3-(Vy)Li)阴离子分别转化为氢化异构体[(tBu3SiN=)3WVy]Na(2-VyNa)和[(tBu3SiN=3WEt]Li(2-etli))。报道了3-(NBU)Li的结构，并讨论了Bu3SiX配位(X=O，NH，N)体系的钨-氢化物耦合常数。
Treatment of (tBu3SiNH)(tBu3SiN=)2WH (1‐H) with small alkyl anions (RM) afforded tungsten alkyl hydride anions [(tBu3SiNH)(tBu3SiN=)2HWR)]M (3‐(R)M: R=CH3, M=Li; R=nBu, M=Li; R=neoPe, M=Li; R=CH2Ph (Bn), M=K (two isomers); R=CCH, M=Na; R=CH=CH2(Vy), M=Li). The saturated alkyl anions3‐(R)M (3‐(R)M: R=CH3, M=Li; R=nBu, M=Li; R=neoPe, M=Li; R=CH2Ph (Bn), M=K) degraded via apparent 1,2‐RH‐elimination to produce the known [(tBu3SiN=)3WH]M (2‐HM), but the acetylide (3‐(C2H)Na) and vinyl (3‐(Vy)Li) anions converted to their hydrogenated isomers, [(tBu3SiN=)3WVy]Na (2‐VyNa) and [(tBu3SiN=)3WEt]Li (2‐EtLi), respectively. The structure of3‐(nBu)Li is reported, and a discussion of tungsten‐hydride coupling constants intBu3SiX‐ligated (X=O, NH, N) systems is given.