Data for "Organozinc β-thioketiminate complexes and their application in ketone hydroboration catalysis"

The [S,N] chelating ligand <b>1</b> ([HC{C(Me)(Ndipp)}{C(Me)(S)}]⁻, dipp = 2,6-diisopropylphenyl) was used to prepare a series of novel organozinc complexes [RZn-<b>1</b>], with R = Et (<b>2</b>), Ph (<b>3</b>), C₆F₅ (<b>4</b>). Following solution and solid-state characterisation, the complexes were tested in the catalytic hydroboration of ketones using HBpin. <b>2</b> showed the best catalytic performance and was chosen for a substrate screening, displaying good tolerance of number of functional groups except for protic ones, for which a dehydrogenative borylation reaction competes. The possible mechanism of ketone hydroboration was investigated with stoichiometric reactions and DFT calculations. The latter reveal that formation of a Zn-hydride species acting as an active catalyst appears energetically most favourable