Isolation of a C3-metalated indolizine complex and a phosphonium ring-fused bicyclic metallafuran from the osmium-induced transformation of pyridine-tethered alkynes.,Faraday Discussions

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Isolation of a C3-metalated indolizine complex and a phosphonium ring-fused bicyclic metallafuran from the osmium-induced transformation of pyridine-tethered alkynes.
Faraday Discussions ( IF 3.3 ) Pub Date : 2019-12-02 , DOI: 10.1039/c9fd00048h
Lai-Hon Chung ₁ , Chi-Fung Yeung , Hau-Lam Shek , Chun-Yuen Wong

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The first C3-metalated indolizine complex was prepared from the reaction between cis-[Os(dppm)2Cl2] (dppm = 1,1-bis(diphenylphosphino)methane) and propargylic pyridine, HC[triple bond, length as m-dash]CC(OH)(2-py)2. A phosphonium ring-fused bicyclic osmafuran complex was also prepared from the reaction between cis-[Os(dppm)2Cl2] and pyridyl ynone, HC[triple bond, length as m-dash]C(C[double bond, length as m-dash]O)(2-py). The formation of these two products revealed the intermediacy of metal-vinylidene species regarding [Os(dppm)2Cl]+-mediated alkyne transformations. Comparison of the d6 transition-metal precursors employed to activate HC[triple bond, length as m-dash]CC(OH)(2-py)2 suggests that precursors with higher π-basicity favor the vinylidene-involving pathway.

中文翻译：

从诱导的吡啶系链炔烃的转化中分离出C3金属化的吲哚嗪络合物和phospho环稠合的双环金属呋喃。

由顺式-[Os（dppm）2Cl2]（dppm = 1,1-双（二苯基二膦基）甲烷）与炔丙基吡啶，HC [三键，长度为m-破折号]之间的反应制备了第一个C3金属化的吲哚嗪络合物CC（OH）（2-py）2。还从顺式[Os（dppm）2Cl2]与吡啶基炔酮之间的反应制备了ring环稠合的双环奥马呋喃配合物，HC [三键，长度为m-破折号C（C [双键，长度为m-破折号] O）（2-py）。这两种产物的形成揭示了金属亚乙烯基与[Os（dppm）2Cl] +介导的炔烃转化有关。用来激活HC三键的d6过渡金属前体的比较，长度为m-虚线CC（OH）（2-py）2，表明具有较高π-碱性的前体有利于亚乙烯基参与的途径。

更新日期：2019-12-04

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