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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.