Attempts toward a Silyl-Stabilized Dicoordinate Borylene: Insertion of Carbon Dioxide into the B-Si Bond.

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-03-26 eCollection Date: 2025-04-14 DOI:10.1021/acs.organomet.5c00050

Kasperi M Salonen, J Mikko Rautiainen, Aaron Mailman, Chris Gendy, Heikki M Tuononen

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引用次数: 0

Abstract

One-electron reduction of the carbene-stabilized borane (Me₂-cAAC)B(Cl)₂Si(SiMe₃)₃, 1, with potassium naphthalenide gave the radical (Me₂-cAAC)B(Cl)Si(SiMe₃)₃, 2. A subsequent one-electron reduction of 2 yielded the dicoordinate borylene (Me₂-cAAC)BSi(SiMe₃)₃, 3, which rapidly underwent intramolecular C-H activation to give cyclo-(Me₂-cAAC)B(H)Si(SiMe₃)₃, 4, irrespective of the employed reaction conditions. Compound 3 could be stabilized as the carbonyl complex (Me₂-cAAC)B(CO)Si(SiMe₃)₃, 5, that gave 4 upon irradiation with a UV light under a CO₂ atmosphere. In contrast, the two-electron reduction of 1 under an atmosphere of CO₂ yielded a mixture of products of which (Me₂-cAAC)B(Cl)(H)C(O)OSi(SiMe₃)₃, 6, could be separated and structurally characterized. Compound 6 is a rare example of CO₂ insertion into a B-E (E = heavier main group element) bond in which boron functions as a nucleophile, thereby mimicking transition metal-mediated carboxylation. The mechanism for the formation of 6 from the purported boryl anion intermediate [(Me₂-cAAC)B(Cl)Si(SiMe₃)₃]^-, 2 ^-, was analyzed computationally.

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对硅基稳定的二坐标硼炔的尝试：二氧化碳插入到B-Si键。

碳稳定硼烷（Me2-cAAC）B(Cl)2Si(SiMe3) 3,1与萘化钾单电子还原得到自由基（Me2-cAAC）B(Cl)Si(SiMe3) 3,2。随后的2的单电子还原得到二配位的硼炔（Me2-cAAC）BSi(SiMe3) 3,3，并迅速进行分子内C-H活化，得到环-(Me2-cAAC)B(H)Si(SiMe3) 3,4，而不考虑所采用的反应条件。化合物3可以稳定为羰基配合物（Me2-cAAC）B(CO)Si(SiMe3) 3,5，在CO2气氛下紫外照射后得到4。相比之下，1在CO2气氛下的双电子还原得到的产物混合物（Me2-cAAC）B(Cl)(H)C(O)OSi(SiMe3) 3,6可以分离并进行结构表征。化合物6是一个罕见的例子，二氧化碳插入到B-E （E =较重的主族元素）键中，其中硼作为亲核试剂起作用，从而模拟过渡金属介导的羧基化。计算分析了硼基阴离子中间体[(Me2-cAAC)B(Cl)Si(SiMe3)3]-， 2-生成6的机理。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.