Phosphinoborylenes as stable sources of fleeting borylenes,Chemical Science

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Phosphinoborylenes as stable sources of fleeting borylenes
Chemical Science ( IF 7.6 ) Pub Date : 2020-09-10 , DOI: 10.1039/d0sc04826g
Conor Pranckevicius _{1,

2} , Marco Weber _{1,

2} , Ivo Krummenacher _{1,

2} , Ashwini K Phukan ₃ , Holger Braunschweig _{1,

2}

Affiliation

Base-stabilised borylenes that mimic the ability of transition metals to bind and activate inert substrates have attracted significant attention in recent years. However, such species are typically highly reactive and fleeting, and often cannot be isolated at ambient temperature. Herein, we describe a readily accessible trimethylphosphine-stabilised borylborylene which was found to possess a labile P–B bond that reversibly cleaves upon gentle heating. Exchange of the labile phosphine with other nucleophiles (CO, isocyanide, 4-dimethylaminopyridine) was investigated, and the binding strength of a range of potential borylene “ligands” has been evaluated computationally. The room-temperature-stable PMe₃-bound borylenes were subsequently applied to novel bond activations including [2 + 2] cycloaddition with carbodiimides and the reduction of dichalcogenides, revealing that PMe₃-stabilised borylenes can effectively behave as stable sources of the analogous fleeting dicoordinate species under mild conditions.

中文翻译：

膦基硼烯作为短暂的硼烯的稳定来源

近年来，模拟过渡金属结合和活化惰性底物的能力的碱稳定硼烯引起了人们的广泛关注。然而，此类物质通常具有高反应性且转瞬即逝，并且通常无法在环境温度下分离。在此，我们描述了一种容易获得的三甲基膦稳定的硼基硼烯，它被发现具有不稳定的 P-B 键，在温和加热时可逆裂解。研究了不稳定膦与其他亲核试剂（CO、异氰化物、4-二甲基氨基吡啶）的交换，并通过计算评估了一系列潜在的亚硼基“配体”的结合强度。室温稳定的 PMe ₃结合的硼烯随后被应用于新型键活化，包括与碳二亚胺的 [2 + 2] 环加成和二硫属化物的还原，表明 PMe ₃稳定的硼烯可以有效地充当类似的短暂的稳定源温和条件下的双配位物种。

更新日期：2020-09-23

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