Visible light driven generation and alkyne insertion reactions of stable bis-cyclometalated Pt(IV) hydrides,Chemical Science

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Visible light driven generation and alkyne insertion reactions of stable bis-cyclometalated Pt(IV) hydrides
Chemical Science ( IF 7.6 ) Pub Date : 2020-10-13 , DOI: 10.1039/d0sc04879h
Dionisio Poveda _{1,

2,

3,

4,

5} , Ángela Vivancos _{1,

2,

3,

4,

5} , Delia Bautista _{3,

4,

5,

6} , Pablo González-Herrero _{1,

2,

3,

4,

5}

Affiliation

Hydride complexes resulting from the oxidative addition of C–H bonds are intermediates in hydrocarbon activation and functionalization reactions. The discovery of metal systems that enable their direct formation through photoexcitation with visible light could lead to advantageous synthetic methodologies. In this study, easily accessible dimers [Pt₂(μ-Cl)₂(C^N)₂] (C^N = cyclometalated 2-arylpyridine) are demonstrated as a very convenient source of Pt(C^N) subunits, which promote photooxidative C–H addition reactions with different 2-arylpyridines (N′^C′H) upon irradiation with blue light. The resulting [PtH(Cl)(C^N)(C′^N′)] complexes are the first isolable Pt(IV) hydrides arising from a cyclometalation reaction. A transcyclometalation process involving three photochemical steps is elucidated, which occurs when the C^N ligand is a monocyclometalated 2,6-diarylpyridine, and a detailed analysis of the photoreactivity associated with the Pt(C^N) moiety is provided. Alkyne insertions into the Pt–H bond of a photogenerated Pt(IV) hydride are also reported as a demonstration of the ability of this class of compounds to undergo subsequent organometallic reactions.

中文翻译：

稳定的双环金属化Pt（IV）氢化物的可见光驱动生成和炔烃插入反应

由C–H键的氧化加成形成的氢化物络合物是烃活化和官能化反应的中间体。金属系统的发现使得能够通过可见光的光激发直接形成金属系统，这可能会带来有利的合成方法。在这项研究中，容易获得的二聚体[Pt ₂（μ-Cl）₂（C ^ N）₂ ]（C ^ N =环金属化的2-芳基吡啶）被证明是Pt（C ^ N）亚基的一种非常方便的来源。在蓝光照射下促进与不同的2-芳基吡啶（N'^ C'H）发生光氧化CH加成反应。所得的[PtH（Cl）（C ^ N）（C'^ N'）]络合物是第一个可分离的Pt（IV）由环金属化反应产生的氢化物。阐明了涉及三个光化学步骤的跨环金属化过程，该过程在C ^ N配体为单环金属化的2,6-二芳基吡啶时发生，并提供了与Pt（C ^ N）部分相关的光反应性的详细分析。还报道了将炔烃插入光生Pt（IV）氢化物的Pt-H键中，以证明此类化合物能够进行后续的有机金属反应。

更新日期：2020-10-17

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