The tris(2-pyridylthio)methyl ligand, [Tptm], affords a variety of metallacarbatranes, i.e. atrane compounds that feature a transannular M�C bond.  Application of this ligand to zinc chemistry allows isolation of interesting organozinc compounds that feature terminal hydride, fluoride or bicarbonate ligands.  Depending upon the nature of the substituent, [Tptm]ZnX may adopt either a classic k4-atrane structure (X = F, HCO3) or a k3-motif (X = H).  These organozinc compounds exhibit interesting reactivity.  For example, [Tptm]ZnH is a catalyst for hydrosilylation of CO2, while the fluoride ligand of [k4-Tptm]ZnF is not only susceptible to coordination by B(C6F5)3 to give the adduct [k4-Tptm]ZnFB(C6F5)3, but it is also an effective hydrogen bond and halogen bond acceptor.  Interesting reactivity of these compounds include (i) the ability of the hydride complex [Tptm]ZnH to serve as a catalyst for hydrosilylation of CO2 and (ii) the ability of the fluoride ligand of [k4-Tptm]ZnF to serve as an effective hydrogen bond and halogen bond acceptor.

Zincacarbatranes:  Organozinc compounds that feature terminal hydride, fluoride and bicarbonate ligands

247th National Meeting (2014)

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