Synthesis and Characterization of a Linear, Two-Coordinate Pt(II) Ketimide Complex
Synthesis and Characterization of a Linear, Two-Coordinate Pt(II) Ketimide Complex
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DOI：
10.1021/acs.inorgchem.9b02443
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发表时间：
2019-12-02
影响因子：
4.6
通讯作者：
Hayton, Trevor W.
中科院分区：
文献类型：
--
作者：
Cook, Andrew W.;Hrobarik, Peter;Hayton, Trevor W.
本文报道了一种线性二配位的Pt（II）酮亚胺配合物Pt（N=（CBu 2）-Bu-t）（2）（1）的合成和表征，该配合物是由PtCl 2（1，5-COD）与2当量的Li（N=（CBu 2）-Bu-t）反应生成的。在反应中还生成了双金属配合物[（（Bu 2C）-Bu-t=N）Pt（mu-N，C-N=C（Bu-t）C-（Me）（2）CH 2）Pt（N=（CBu 2）-Bu-t）]（2）。配合物1和2已通过NMR光谱和X-射线晶体学表征。值得注意的是，复合物1表现出短Pt-N距离（ay. Pt-N = 1.817埃）和具有大（1）J（Pt-195，N-14）耦合常数（537 Hz）的异常去屏蔽Pt-195化学位移（δ（Pt）= -629 ppm）。这些数据结合详细的密度泛函理论电子结构分析，揭示了由sigma-捐赠、pi-捐赠和pi-回馈组合形成的高度共价Pt=N多重键的存在。
Herein we report the synthesis and characterization of a linear, two -coordinate Pt(II) ketimide complex, Pt(N=(CBu2)-Bu-t)(2) (1), formed via the reaction of PtCl2(1,5-COD) with 2 equiv of Li(N=(CBu2)-Bu-t). Also generated in the reaction is the bimetallic complex [((Bu2C)-Bu-t=N)Pt(mu-N,C-N=C(Bu-t)C-(Me)(2)CH2)Pt(N=(CBu2)-Bu-t)] (2). Both complexes 1 and 2 have been characterized by NMR spectroscopy and X-ray crystallography. Notably, complex 1 exhibits short Pt-N distances (ay. Pt-N = 1.817 angstrom) and an unusually deshielded Pt-195 chemical shift (delta(Pt) = -629 ppm) with a large (1)J(Pt-195,N-14) coupling constant (537 Hz). These data, in combination with a detailed density functional theory electronic structure analysis, reveal the presence of highly covalent Pt=N multiple bonds formed by a combination of sigma-donation, pi-donation, and pi-backdonation.