Calcium Hydride Cation [CaH] +  Stabilized by an NNNN‐type Macrocyclic Ligand: A Selective Catalyst for Olefin Hydrogenation | Zendy

Schuhknecht Danny | Zendy; Lhotzky Carolin | Zendy; Spaniol Thomas P. | Zendy; Maron Laurent | Zendy; Okuda Jun | Zendy

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

Author(s) -

Schuhknecht Danny,

Lhotzky Carolin,

Spaniol Thomas P.,

Maron Laurent,

Okuda Jun

Publication year - 2017

Publication title -

angewandte chemie international edition

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 5.831

H-Index - 550

eISSN - 1521-3773

pISSN - 1433-7851

DOI - 10.1002/anie.201706848

Subject(s) - chemistry , hydrogenolysis , hydride , ligand (biochemistry) , cationic polymerization , olefin fiber , medicinal chemistry , nuclear magnetic resonance spectroscopy , catalysis , calcium , inorganic chemistry , crystallography , stereochemistry , hydrogen , polymer chemistry , organic chemistry , biochemistry , receptor

Reaction of dibenzyl calcium complex [Ca(Me 4 TACD)(CH 2 Ph) 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 [Ca 2 H 2 (Me 4 TACD) 2 ](PhCHSiPh 3 ) 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)(CH 2 Ph)(thf)] + gave dicationic calcium hydrides [Ca 2 H 2 (Me 4 TACD) 2 ][BAr 4 ] 2 (Ar=C 6 H 4 ‐4‐ t Bu; C 6 H 3 ‐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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