Kyle Pearce (@kylegpearce.bsky.social)

Our latest paper investigating Calcium-Zinc cooperativity is just out in Organometallics. Pleasure to see Marcos get stuck into this during his time at @bathchem.bsky.social, Vamos! pubs.acs.org/doi/10.1021/...

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Calcium Alkynyl(hydrido)zincates 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-C≡CR)(μ-TMP)Zn(μ-H)]2 (R = nBu, 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-C≡CnBu)2Zn(μ-H)]2 and [(BDI)Ca(μ-C≡CPh)2Zn(μ-C≡CPh)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-C≡CnBu)(μ-TMP)Zn(μ-H)]2 and PhC≡CH, provided [(THF)2Ca(μ-C≡CPh)3Zn(CH2Ph)]2, resulting from toluene activation and after addition of THF as the only identifiable product. https://pubs.acs.org/doi/10.1021/acs.organomet.6c00164