形式二镍钴(I)氢化物阳离子的可逆 C-CN 键裂解作用

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Organometallics Pub Date : 2024-11-01 DOI:10.1021/acs.organomet.4c0034010.1021/acs.organomet.4c00340

Yu Cao, Neil A. Dodd, John Bacsa and Joseph P. Sadighi*,

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引用次数: 0

摘要

一种 N-杂环碳烯 (NHC) 配体支持一个稳定的 [Ni2H]+ 核心，正式名称为二镍 (I)。这种二磁性阳离子复合物具有弯曲的氢化物桥和 2.9926(5) Å 的 Ni-Ni 间距，大于两个共价半径。该阳离子具有弱质子性，在强碱作用下会发生去质子化反应，形成相应的 (NHC)nickel(0) 二聚体。它与脂肪族腈反应会导致 C-CN 键断裂。该反应的有机产物表明，这一断键步骤涉及活性镍烷基中间体，并且是可逆的。

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Reversible C–CN Bond Cleavage by a Formal Dinickel(I) Hydride Cation

An N-heterocyclic carbene (NHC) ligand supports a stable [Ni₂H]⁺ core, formally dinickel(I). This diamagnetic cation complex features a bent hydride bridge and a Ni···Ni distance, 2.9926(5) Å, larger than two covalent radii. The cation displays weakly protic character, undergoing deprotonation by strong base to form the corresponding (NHC)nickel(0) dimer. Its reaction with aliphatic nitriles results in C–CN bond cleavage. The organic products of this reaction suggest that this bond-breaking step involves reactive nickel alkyl intermediates and occurs reversibly.

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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.