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Calcium Alkynyl(hydrido)zincates
Marcos López-Aguilar1,2, Kyle G Pearce1, Michael S Hill1
1Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
Abstract:
The β-diketiminato calcium hydride dimer, [(BDI)-CaH]2 (BDI = HC-{(Me)-CNDipp}2; Dipp = 2,6-i-Pr2C6H3), reacts with [ZnTMP2] in the presence of terminal alkynes to provide a structurally diverse series of heterobimetallic calcium-zinc acetylide derivatives. Reactions employing two equivalents of alkyne yield the dialkynyl-(hydrido)-zincates, [(BDI)-Ca-(μ-CCR)-(μ-TMP)-Zn-(μ-H)]2 (R = n Bu, Ph), which undergo ligand redistribution to afford the corresponding β-diketiminato calcium acetylides. Conversely, use of four equivalents of alkyne results in further substitution at zinc to provide the tetrakis-(alkynyl)-zincates, [(BDI)-Ca-(μ-CC n Bu)2Zn-(μ-H)]2 and [(BDI)-Ca-(μ-CCPh)2Zn-(μ-CCPh)2Ca-(BDI)]. In contrast, an attempt to synthesize a similarly higher order calcium zincate but containing differentiated alkynyl substituents, by reaction of [(BDI)-Ca-(μ-CC n Bu)-(μ-TMP)-Zn-(μ-H)]2 and PhCCH, provided [(THF)2Ca-(μ-CCPh)3Zn-(CH2Ph)]2, resulting from toluene activation and after addition of THF as the only identifiable product.
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