Abstract: A new series of titanium(IV) and zirconium(IV) amides have been prepared from the reaction between M(NMe2)4 (M=Ti, Zr) and C 2-symmetric ligands, (R)-2,2′-bis(pyridin-2-ylmethylamino)-6,6′-dimethyl-1,1′-biphenyl (2H2), (R)-2,2′-bis(pyrrol-2-ylmethyleneamino)-6,6′-dimethyl-1,1′-biphenyl (3H2), (R)-2,2′-bis(diphenylphosphinoylamino)-6,6′-dimethyl-1,1′-biphenyl (4H2), (R)-2,2′-bis(methanesulphonylamino)-6,6′-dimethyl-1,1′-biphenyl (5H2), (R)-2,2′-bis(p-toluenesulphonylamino)-6,6′-dimethyl-1,1′-biphenyl (6H2), and C 1-symmetric ligands, (R)-2-(diphenylthiophosphoramino)-2′-(dimethylamino)-6,6′-dimethyl-1,1′-biphenyl (7H) and (R)-2-(pyridin-2-ylamino)-2′-(dimethylamino)-6,6′-dimethyl-1,1′-biphenyl (8H), which are derived from (R)-2,2′-diamino-6,6′-dimethyl-1,1′-biphenyl. Treatment of M(NMe2)4 with 1 equiv. of N4-ligand, 2H2 or 3H2 gives, after recrystallization from an n-hexane solution, the chiral zirconium amides (2)Zr(NMe2)2 (9), (3)Zr(NMe2)2 (11), and titanium amide (3)Ti(NMe2)2 (10), respectively, in good yields. Reaction of Zr(NMe2)4 with 1 equiv of diphenylphosphoramide 4H2 affords the chiral zirconium amide (4)Zr(NMe2)2 (12) in 85% yield. Under similar reaction conditions, treatment of Ti(NMe2)4 with 1 equiv. of sulphonylamide ligand, 5H2 or 6H2 gives, after recrystallization from a toluene solution, the chiral titanium amides (5)Ti(NMe2)2·0.5C7H8 (13·0.5C7H8) and (6)Ti(NMe2)2 (15), respectively, in good yields, while reaction of Zr(NMe2)4 with 1 equiv. of 5H2 or 6H2 gives the bis-ligated complexes, (5)2Zr (14) and (6)2Zr (16). Treatment of M(NMe2)4 with 2 equiv. of diphenylthiophosphoramide ligand 7H or N3-ligand 8H gives, after recrystallization from a benzene solution, the bis-ligated chiral zirconium amides (7)2Zr(NMe2)2 (17) and (8)2Zr(NMe2)2 (19), and bis-ligated chiral titanium amide (8)2Ti(NMe2)2 (18), respectively, in good yields. All new compounds have been characterized by various spectroscopic techniques, and elemental analyses. The solid-state structures of complexes 10, 12, 13, and 17–19 have further been confirmed by X-ray diffraction analyses. The zirconium amides are active catalysts for the asymmetric hydroamination/cyclization of aminoalkenes, affording cyclic amines in good to excellent yields with moderate ee values, while the titanium amides are not. [Copyright &y& Elsevier]