Multimetallic Alkaline-Earth Hydride Cations

Lucia Garcia; Mary F. Mahon; Michael S. Hill

doi:10.1021/acs.organomet.9b00493

Multimetallic Alkaline-Earth Hydride Cations

Lucia Garcia, Mary F. Mahon, Michael S. Hill

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

14 Citations (SciVal)

18 Downloads (Pure)

Abstract

Reactions of dimeric β-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 μ₂-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}₂H]⁺ 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.

Original language	English
Pages (from-to)	3778-3785
Number of pages	8
Journal	Organometallics
Volume	38
Issue number	19
Early online date	9 Sep 2019
DOIs	https://doi.org/10.1021/acs.organomet.9b00493
Publication status	Published - 14 Oct 2019

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/acs.organomet.9b00493

Multimetallic Alkaline Earth Hydride Cations_OM_revsion.PDF
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.organomet.9b00493
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title = "Multimetallic Alkaline-Earth Hydride Cations",

abstract = "Reactions of dimeric β-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 μ2-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}2H]+ 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.",

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N2 - Reactions of dimeric β-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 μ2-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}2H]+ 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.

AB - Reactions of dimeric β-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 μ2-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}2H]+ 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.

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Multimetallic Alkaline-Earth Hydride Cations

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Augmentation of Alkaline Earth Reactivity: An FLP Analogy

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Multimetallic Alkaline-Earth Hydride Cations

Abstract

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Augmentation of Alkaline Earth Reactivity: An FLP Analogy

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