Abstract
The dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CN-2,6-i-Pr2C6H3}2), reacts with terminal alkenes to provide the corresponding alkyl derivatives. With 1-octene, 3,3-dimethyl-1-butene, 3-phenyl-1-propene, and 4-phenyl-1-butene, the ultimate products are dimeric alkyl species, which form sequentially via dinuclear calcium hydrido-alkyl intermediates. Reaction of diphenylacetylene with [(BDI)CaH]2 provides a tetra-calcium complex in which a stilbene dianion bridges symmetrically between two hydrido-bridged bis-β-diketiminato calcium units, while treatment with trans-stilbene yields a dicalcium benzyl-hydride derivative, [{(BDI)Ca}2(H)(PhCHCH2Ph)]. Reaction of [(BDI)CaH]2 and 1,5-hexadiene has previously been observed to provide facile 5-exo-trig cyclization to calcium cyclopentylmethyl derivatives. In contrast, analogous reaction with 1,7-octadiene provides exclusive intermolecular insertion to yield a dimeric open chain calcium oct-7-en-1-yl derivative. Reaction with the internal alken...
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