烷基锌介导氢化钙的金属转化

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2025-05-07 DOI:10.1039/d5dt00958h

Kyle G. Pearce, Mary F Mahon, Michael Hill

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引用次数: 0

摘要

二聚体β-二酮酸氢化钙，[(BDI)CaH]2 (BDI = HC{(Me)CNDipp}2；Dipp = 2,6-i- pr2c6h3)，与二烷基锌试剂以1:2的比例反应，通过顺序的二烷基（氢化）锌酸盐形成，烷基钙挤压，然后是有机基和观察BDI配体的进一步不可逆金属化，证明了这种金属化策略在获得烷基钙或烷基锌缀合物方面的通通性。当二甲基锌与预安装有芳基取代基的有机钙二聚体[(BDI)Ca(μ-3,5- tbu2c6h3)(μ-H)Ca(BDI)]反应时，可通过氢化物-甲基交换得到烷基官能团和芳基官能团分化的有机钙二聚体[(BDI)Ca(μ-3,5- tbu2c6h3)(μ-Me)Ca(BDI)]。

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Alkylzinc-Mediated Transmetallation of a Calcium Hydride

The dimeric β-diketiminato calcium hydride, [(BDI)CaH]₂ (BDI = HC{(Me)CNDipp}₂; Dipp = 2,6-i-Pr₂C₆H₃), reacts with dialkylzinc reagents in a 1:2 ratio through sequential dialkyl(hydrido)zincate formation, calcium alkyl extrusion followed by further irreversible transmetallation of both the organyl and spectator BDI ligands, demonstrating the generality of this transmetallation strategy to access calcium alkyls or ligated zinc alkylated species. When the reaction is performed with dimethyl zinc and an organocalcium dimer with a pre-installed kinetically stabilising aryl substituent, [(BDI)Ca(μ-3,5-^tBu₂C₆H₃)(μ-H)Ca(BDI)], an organocalcium dimer comprised of differentiated alkyl and aryl functionalities can be accessed through hydride-for-methyl exchange, [(BDI)Ca(μ-3,5-^tBu₂C₆H₃)(μ-Me)Ca(BDI)].

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来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.