Calcium Hydride Cation [CaH](+) Stabilized by an NNNN-type Macrocyclic Ligand: A Selective Catalyst for Olefin Hydrogenation - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Angewandte Chemie International Edition Year : 2017

Calcium Hydride Cation [CaH](+) Stabilized by an NNNN-type Macrocyclic Ligand: A Selective Catalyst for Olefin Hydrogenation

Abstract

Reaction of dibenzyl calcium complex [Ca(Me(4)TACD)(CH2Ph)(2)], containing the neutral NNNN-type macrocyclic ligand Me(4)TACD (Me(4)TACD=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane), with triphenylsilane gave the cationic dinuclear calcium hydride [Ca2H2(Me(4)TACD)(2)](PhCHSiPh3)(2) which was characterized by NMR spectroscopy and single-crystal X-ray diffraction. The cation can be regarded as the ligand-stabilized dimeric form of hypothetical [CaH](+). Hydrogenolysis of benzyl calcium cation [Ca(Me(4)TACD)(CH2Ph)(thf)](+) gave dicationic calcium hydrides [Ca2H2(Me(4)TACD)(2)][BAr4](2) (Ar=C6H4-4-Bu-t; C6H3-3,5-Me-2) containing weakly coordinating anions. In THF, they catalyzed the isotope exchange of H-2 and D-2 to give HD and the hydrogenation of unactivated 1-alkenes.
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Dates and versions

hal-01961163 , version 1 (19-12-2018)

Identifiers

  • HAL Id : hal-01961163 , version 1

Cite

Danny Schuhknecht, Carolin Lhotzky, Thomas P. Spaniol, Laurent Maron, Jun Okuda. Calcium Hydride Cation [CaH](+) Stabilized by an NNNN-type Macrocyclic Ligand: A Selective Catalyst for Olefin Hydrogenation. Angewandte Chemie International Edition, 2017, 56 (40), pp.12367--12371. ⟨hal-01961163⟩
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