Photoinduced One-Pot Synthesis of a Chromium Germylyne Complex and Its Formation Mechanism
Photoinduced One-Pot Synthesis of a Chromium Germylyne Complex and Its Formation Mechanism
复制标题
光诱导一锅法合成铬锗炔配合物及其形成机制
DOI：
10.1021/acs.organomet.2c00594
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发表时间：
2023
期刊：
影响因子：
2.8
通讯作者：
Hashimoto Hisako
中科院分区：
文献类型：
--
作者：
Nagata Koichi;Omura Hirotaka;Matsuoka Masahiro;Tobita Hiromi;Hashimoto Hisako
通过甲基铬配合物[Cp*Cr（CO）3 Me]与三氢锗烷（TsiGeH 3）的光化学反应，直接合成了一种含Cr <$Ge三键的铬锗炔配合物[Cp*（OC）2Cr <$GeTsi]（1）（Tsi = C（SiMe 3）3）.通过NMR对反应的详细监测表明，在紫外-可见光照射下，首先形成了一个中间体--中间体2是从另一个实验中分离出来的，在蓝色LED光照射下。化合物1和2的结构经X-射线单晶衍射证实。基于对中间体2吸收带的TD-DFT计算分析，提出了中间体2释放氢生成中间体1的可能机制，包括通过削弱Cr-Ge多重键形成金属锗烯的过程.
A chromium germylyne (or germylidyne) complex having a Cr≡Ge triple bond, [Cp*(OC)2Cr≡GeTsi] (1) (Tsi = C(SiMe3)3), was directly synthesized by the photochemical reaction of a methyl chromium complex [Cp*Cr(CO)3Me] and a trihydrogermane (TsiGeH3). Detailed monitoring the reaction by NMR revealed the initial formation of hydrido (hydrogermylene) complex [Cp*(OC)2(H)Cr═Ge(H)Tsi] (2) as an intermediate and its facile release of dihydrogen to afford1under UV–vis light irradiation. The intermediate2was isolated from another experiment under blue LED light irradiation. The structures of1and2were confirmed by X-ray crystallography. Based on the analysis of absorption bands of intermediate2using TD-DFT calculations, we suggest possible mechanisms for releasing dihydrogen from2to afford1, which includes a process forming a metallogermylene by weakening the Cr–Ge multiple bond.