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Synthesis and Reactivity of Discrete Calcium Imides
Author(s) -
Wolf Benjamin M.,
MaichleMössmer Cäcilia,
Anwander Reiner
Publication year - 2016
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.201607608
Subject(s) - reactivity (psychology) , calcium , chemistry , materials science , organic chemistry , medicine , alternative medicine , pathology
Protonolysis of dibenzylcalcium with triphenylsilylamine affords a thf‐coordinated tetrametallic calcium imide with a heterocuboid core structure. The use of calcium bis(tetramethylaluminate) as a precursor for tandem salt metathesis/protonolysis reactions with alkali metal amides of 2,6‐diisopropylaniline and triphenylsilylamine provides access to Lewis acid stabilized monocalcium imides of the type [(thf) 4 Ca(μ 2 ‐NR)(μ 2 ‐Me)AlMe 2 ]. Treatment of [(thf) 4 Ca(μ 2 ‐NSiPh 3 )(μ 2 ‐Me)AlMe 2 ] with phenylsilane results in H−Si addition across the Ca−N imido bond, producing a homoleptic calcium amidoaluminate complex and putative CaH 2 whereas reaction with phenylacetylene leads to protonation of an AlMe moiety to yield the dimeric complex [(thf)Ca{NSiPh 3 }{AlMe 2 (CCPh)}] 2 .