2026-10-11T22:38:29Z https://api.figshare.com/v2/oai

oai:figshare.com:article/30720416 2026-09-30T08:34:16Z category_31853 portal_403 item_type_3 month_year_09_2026

Data for "Aldehyde Hydrosilylation with Ethylzinc Complexes of Bulky β‐Thioketiminate Ligands" Jamie Allen (10296766) Samuel J. H. Gaughan (21727289) Kuldip Singh (1362372) Tobias Kramer (1289145) Alexander F. R. Kilpatrick (3594317) Inorganic chemistry zinc catalysis <p dir="ltr">The synthesis of a novel <i>β</i>-thioketiminate ligand, H-SacNac^Ar* (<b>3</b>), featuring a bulky 2,6-bis(benzhydryl)-4-methylphenyl substituent, and its zinc ethyl complex [(SacNac^Ar*)ZnEt] (<b>4</b>), is reported. Complex <b>4</b> catalyzes the hydrosilylation of benzaldehyde with PhSiH₃, showing enhanced activity relative to the less bulky analogue [(SacNac^Dipp)ZnEt] <b>2</b>, particularly upon addition of MeOH as an activator. Under these conditions, <b>4</b> exhibits high selectivity toward dialkoxysilane product (<b>B),</b> over monoalkoxysilane (<b>A</b>) or trialkoxysilane (<b>C</b>) products. Density functional theory calculations support a mechanism involving precatalyst activation by MeOH to form a zinc alkoxide intermediate, followed by <i>σ</i>-bond metathesis with PhSiH₃ affording a catalytically active zinc hydride complex. The results highlight the role of ligand sterics and alcohol activators in tuning catalytic activity and offer insights into the design of new zinc-based hydrosilylation catalysts.</p> 2025-11-25T00:00:00Z Dataset Dataset 10.25392/leicester.data.29574776 https://figshare.com/articles/dataset/Data_for_Aldehyde_Hydrosilylation_with_Ethylzinc_Complexes_of_Bulky_Thioketiminate_Ligands_/30720416 CC BY 4.0