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硅基稳定的双配位硼烯的研究尝试：二氧化碳插入硼-硅键的反应

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

作者信息

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

机构信息

Department of Chemistry, NanoScience Center, University of Jyväskylä, P.O. Box 35, Jyväskylä FI-40014, Finland.

出版信息

Organometallics. 2025 Mar 26;44(7):899-904. doi: 10.1021/acs.organomet.5c00050. eCollection 2025 Apr 14.

DOI:10.1021/acs.organomet.5c00050
PMID:40248339
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12002063/
Abstract

One-electron reduction of the carbene-stabilized borane (Me-cAAC)B(Cl)Si(SiMe), , with potassium naphthalenide gave the radical (Me-cAAC)B(Cl)Si(SiMe), . A subsequent one-electron reduction of yielded the dicoordinate borylene (Me-cAAC)BSi(SiMe), , which rapidly underwent intramolecular C-H activation to give cyclo-(Me-cAAC)B(H)Si(SiMe), , irrespective of the employed reaction conditions. Compound could be stabilized as the carbonyl complex (Me-cAAC)B(CO)Si(SiMe), , that gave upon irradiation with a UV light under a CO atmosphere. In contrast, the two-electron reduction of under an atmosphere of CO yielded a mixture of products of which (Me-cAAC)B(Cl)(H)C(O)OSi(SiMe), , could be separated and structurally characterized. Compound is a rare example of CO 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 from the purported boryl anion intermediate [(Me-cAAC)B(Cl)Si(SiMe)], , was analyzed computationally.

摘要

用萘钠对卡宾稳定的硼烷（Me - cAAC）B(Cl)Si(SiMe)₂进行单电子还原，得到自由基（Me - cAAC）B(Cl)Si(SiMe)₂。随后对其进行单电子还原，得到二配位硼烯（Me - cAAC）BSi(SiMe)₂，无论采用何种反应条件，该硼烯都会迅速发生分子内C - H活化，生成环 -（Me - cAAC）B(H)Si(SiMe)₂。化合物 可以稳定为羰基配合物（Me - cAAC）B(CO)Si(SiMe)₂，该配合物在CO气氛下用紫外光照射时会生成 。相比之下，在CO气氛下对 进行双电子还原，得到产物混合物，其中（Me - cAAC）B(Cl)(H)C(O)OSi(SiMe)₂可以分离并进行结构表征。化合物 是CO插入B - E（E = 较重主族元素）键的罕见例子，其中硼作为亲核试剂，从而模拟了过渡金属介导的羧基化反应。通过计算分析了由假定的硼基阴离子中间体[(Me - cAAC)B(Cl)Si(SiMe)]⁻形成 的机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/657ca9d9fcea/om5c00050_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/0f0ff11aba09/om5c00050_0007.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/b5b55b6b61ed/om5c00050_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/2c1f38b5abc5/om5c00050_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/8214e8e519af/om5c00050_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/816e9399fe0a/om5c00050_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/3418117370c1/om5c00050_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/f7c5cce3755b/om5c00050_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/657ca9d9fcea/om5c00050_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/0f0ff11aba09/om5c00050_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/87b93e1a0247/om5c00050_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/b5b55b6b61ed/om5c00050_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/2c1f38b5abc5/om5c00050_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/8214e8e519af/om5c00050_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/816e9399fe0a/om5c00050_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/3418117370c1/om5c00050_0009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/f7c5cce3755b/om5c00050_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9f88/12002063/657ca9d9fcea/om5c00050_0006.jpg

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