Multimetallic Alkaline-Earth Hydride Cations

Multimetallic Alkaline-Earth Hydride Cations
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DOI:
10.1021/acs.organomet.9b00493
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发表时间:
2019-10-14
期刊:
影响因子:
2.8
通讯作者:
Hill, Michael S.
Hill, Michael S.
中科院分区:
化学2区
文献类型:
--
作者:
Garcia, Lucia;Mahon, Mary F.;Hill, Michael S.

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Reactions of dimeric beta-diketiminato (BDI) magnesium and calcium hydrides with [(BDI)Mg](+)[Al{OC(CF3)(3)}(4)](-) provide ionic multimetallic hydride derivatives, which have been characterized by single-crystal X-ray diffraction analysis. The exclusively magnesium centered species comprises a cation in which two [(BDI)Mg](+) units are connected by a single mu(2)-bridging hydride. In contrast, the greater lability of the calcium-containing system is underscored by the isolation of a cyclic heterotrimetallic species in which a CaH2 moiety is coordinated by a molecule of benzene and an aryl substituent of a [{(BDI)Mg}(2)H](+) cation. The homometallic dimagnesium species displays a greater facility toward reaction with diphenylacetylene than neutral [(BDI)MgH](2), although the resultant crystallographically characterized vinyldimagnesium cation equilibrates into a complex mixture of neutral and ionic species in solution. An initial assessment of both systems for the hydrosilylation of 1-hexene and diphenylacetylene evidences an inferior catalytic performance of [(BDI)MgH](2) in isolation.