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Detection of Ylide Formation between an Alkylidenecarbene and Acetonitrile by Femtosecond Transient Absorption Spectroscopy
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-10-07 , DOI: 10.1021/jacs.1c07074 Sujan K Sarkar 1 , Minji Ko 2 , Xueqin Bai 1 , Lili Du 1, 3 , Dasan M Thamattoor 2 , David Lee Phillips 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-10-07 , DOI: 10.1021/jacs.1c07074 Sujan K Sarkar 1 , Minji Ko 2 , Xueqin Bai 1 , Lili Du 1, 3 , Dasan M Thamattoor 2 , David Lee Phillips 1
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Femtosecond laser flash photolysis of 3-(1a,9b-dihydro-1H-cyclopropa[l]phenanthren-1-ylidene)tetrahydrofuran produces singlet 3-oxacyclopentylidenecarbene which reacts with acetonitrile solvent to form an ylide. This is the first direct detection of ylide formation by an alkylidenecarbene. This new type of ylide was observed to have a broad absorption band in the visible region with λmax ∼450 nm and a lifetime of ∼13.5 ps. As with other “conventional” carbenes (the divalent carbon atom is separately bound to two substituents), this ylide formation method could be also useful for detecting alkylidenecarbenes, especially those that do not absorb at wavelengths suitable for direct observation. Furthermore, the mechanisms by which 3-oxacyclopentylidenecarbene forms the ylide and the overall favorability of ylide formation, vis-à-vis ring expansion of the carbene to strained 3-oxacyclohexyne, were supported by results from density functional theory calculations.
中文翻译：
飞秒瞬态吸收光谱法检测亚烷基卡宾和乙腈之间的叶立德形成
飞秒激光闪光光解 3-(1 a ,9 b -dihydro-1 H -cyclopropa[ l ]phenanthren-1-ylidene)四氢呋喃产生单线态 3-oxacyclopentylidenecarbene，其与乙腈溶剂反应形成叶立德。这是第一次直接检测由亚烷基卡宾形成的叶立德。观察到这种新型叶立德在可见光区具有宽吸收带，λ max～450 nm，寿命～13.5 ps。与其他“常规”卡宾（二价碳原子分别与两个取代基结合）一样，这种叶立德形成方法也可用于检测亚烷基卡宾，尤其是在适合直接观察的波长处不吸收的那些。此外，密度泛函理论计算的结果支持了 3-氧杂环戊叉烯卡宾形成叶立德的机制和叶立德形成的总体有利性，相对于卡宾的环膨胀到应变的 3-氧杂环己炔。
更新日期：2021-10-20
中文翻译：
飞秒瞬态吸收光谱法检测亚烷基卡宾和乙腈之间的叶立德形成
飞秒激光闪光光解 3-(1 a ,9 b -dihydro-1 H -cyclopropa[ l ]phenanthren-1-ylidene)四氢呋喃产生单线态 3-oxacyclopentylidenecarbene，其与乙腈溶剂反应形成叶立德。这是第一次直接检测由亚烷基卡宾形成的叶立德。观察到这种新型叶立德在可见光区具有宽吸收带，λ max～450 nm，寿命～13.5 ps。与其他“常规”卡宾（二价碳原子分别与两个取代基结合）一样，这种叶立德形成方法也可用于检测亚烷基卡宾，尤其是在适合直接观察的波长处不吸收的那些。此外，密度泛函理论计算的结果支持了 3-氧杂环戊叉烯卡宾形成叶立德的机制和叶立德形成的总体有利性，相对于卡宾的环膨胀到应变的 3-氧杂环己炔。
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