We report a series of Zn(II) and Cd(II) metal complexes [L12(ZnCl2)] (1), [L12(ZnBr2)] (2), [L12(CdCl2)] (3), [L12(CdI2)] (4), [L22(ZnCl2)] (5), [L22(ZnBr2)] (6), [L22(ZnI2)] (7), [L22(CdCl2)] (8), [L32(CdCl2)] (9) and [L42(ZnBr2)] (10), synthesized using various unsymmetrical aryl thiourea ligands: 1-(2,6-diisopropylphenyl)-3-phenylthiourea (L1), 1-mesityl-3-phenylthiourea (L2), 1-(2-fluorophenyl)-3-phenylthiourea (L3) and symmetrical 1,3-bis(2-fluorophenyl)thiourea (L4). The ligands and metal complexes were characterized by 1H, 13C{1H} NMR, FT-IR analysis. Solid-state structures of the zinc and cadmium metal complexes (1–8) were established using the single-crystal diffraction analysis technique. Furthermore, the catalytic activities of the Zn(II) complexes towards hydroboration of aldehydes and ketones (-C=O) as substrates were studied. Excellent yields of the corresponding boronate esters were achieved. © 2022 Wiley-VCH GmbH.