Visible light induced formation of a tungsten hydride complex
Visible light induced formation of a tungsten hydride complex
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可见光诱导氢化钨络合物的形成
DOI：
10.1039/d2dt03675d
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发表时间：
2023
影响因子：
4
通讯作者：
Dempsey, Jillian L.
中科院分区：
文献类型：
--
作者：
Isaacs, Diane P.;Gruninger, Cole T.;Huang, Tao;Jordan, Aldo M.;Nicholas, Genique;Chen, Chun-Hsing;ter Horst, Marc A.;Dempsey, Jillian L.
当在刘易斯碱（L）存在下用蓝光照射时，[CpW（CO）3]2发生金属-金属键断裂，然后发生歧化反应，形成[CpW（CO）3 L]+和[CpW（CO）3]-。在这里，我们证明了在四氟硼酸吡啶盐的存在下，[CpW（CO）3]−进一步反应形成金属氢化物配合物CpW（CO）3 H。通过原位光1H NMR光谱实验监测反应，并通过确定形成的量子产率研究光驱动氢化物形成的机制。形成CpW（CO）3 H的量子产率与I−1/2（I =我们样品管上的光子通量）相关，表明[CpW（CO）3]2形成氢化物前体[CpW（CO）3]−的净反离子化主要通过自由基链机制发生。
When irradiated with blue light in the presence of a Lewis base (L), [CpW(CO)3]2 undergoes metal–metal bond cleavage followed by a disproportionation reaction to form [CpW(CO)3L]+ and [CpW(CO)3]−. Here, we show that in the presence of pyridinium tetrafluoroborate, [CpW(CO)3]− reacts further to form a metal hydride complex CpW(CO)3H. The rection was monitored through in situ photo 1H NMR spectroscopy experiments and the mechanism of light-driven hydride formation was investigated by determining quantum yields of formation. Quantum yields of formation of CpW(CO)3H correlate with I−1/2 (I = photon flux on our sample tube), indicating that the net disproportionation of [CpW(CO)3]2 to form the hydride precursor [CpW(CO)3]− occurs primarily through a radical chain mechanism.