A bulky, optically active monoanionic scorpionate ligand, tris(4S-isopropyl-5,5-dimethyl-2-oxazolinyl)phenylborate (ToP*), is synthesized from the naturally occurring amino acid l-valine as its lithium salt, Li[ToP*] (1). That compound is readily converted to the thallium complex Tl[ToP*] (2) and to the acid derivative H[ToP*] (3). Group 7 tricarbonyl complexes ToP*M(CO)3(M = Mn (4), Re (5)) are synthesized by the reaction of MBr(CO)5 and Li[ToP*] and are crystallographically characterized. The νCO bands in their infrared spectra indicate that π back-donation in the rhenium compounds is greater with ToP* than with non-methylated tris(4S-isopropyl-2-oxazolinyl)phenylborate (ToP). The reaction of H[ToP*] and ZnEt2 gives ToP*ZnEt (6), while ToP*ZnCl (7) is synthesized from Li[ToP*] and ZnCl2. The reaction of ToP*ZnCl and KOtBu followed by addition of PhSiH3 provides the zinc hydride complex ToP*ZnH (8). Compound 8 is the first example of a crystallographically characterized optically active zinc hydride. We tested its catalytic reactivity in the cross-dehydrocoupling of silanes and alcohols, which provided Si-chiral silanes with moderate enantioselectivity. Disciplines Chemistry CommentsReprinted (adapted) with permission from Organometallics 34 (2015) (5)) are synthesized by the reaction of MBr(CO) 5 and Li[To P *] and are crystallographically characterized. The ν CO bands in their infrared spectra indicate that π back-donation in the rhenium compounds is greater with To P * than with non-methylated tris(4S-isopropyl-2-oxazolinyl)phenylborate (To P ). The reaction of H[To P *] and ZnEt 2 gives To P *ZnEt (6), while To P *ZnCl (7) is synthesized from Li[To P *] and ZnCl 2 . The reaction of To P *ZnCl and KOtBu followed by addition of PhSiH 3 provides the zinc hydride complex To P *ZnH (8). Compound 8 is the first example of a crystallographically characterized optically active zinc hydride. We tested its catalytic reactivity in the cross-dehydrocoupling of silanes and alcohols, which provided Si-chiral silanes with moderate enantioselectivity.