Inserted products of lithium silylquinolylamide dimers [{8-(2-R-C₉H₅N)N(Me₃Si)}Li·OEt₂]₂ (R = H or Me) with dimethylcyanamide and their reactive derivatives with metal halides

Abstract

The insertion reactions of lithium silylquinolylamide dimers [{8-(2-R-C9H5N)N(Me3Si)}Li·OEt2]2 (R = H, 1a; R = Me, 1b) with dimethylcyanamide afforded dimeric lithium 8-quinolylguanidinates [{8-(2-R-C9H5N)NC(NMe2)N(SiMe3)}Li]2 (R = H, 2a; R = Me, 2b) with a cisoid arrangement of the ligands. Further reaction of 2b with MCl2 (M = Co or Fe) formed the eight-membered binuclear metallic 8-quinolylguanidinate complexes [{8-(2-CH3-C9H5N)NC(NMe2)N(SiMe3)}MCl]2 (M = Fe, 3; Co, 4). The reaction of 2a with (MeC5H4)TiCl3 afforded a centrosymmetric dimeric titanium(IV) complex [{8-(C9H6N)NC(NMe2)N}Ti(MeC5H4)Cl]2 (5) via a metathesis reaction and the elimination of SiMe3Cl. The guanidinate ligand 2b was hydrolyzed with an equimolar amount of water, and reacted with (MeC5H4)TiCl3 forming a monoligated half-titanocene compound {8-(2-CH3-C9H5N)N(H)C(NMe2)N}Ti(MeC5H4)Cl2 (6). Therefore lithium silylquinolylamide dimers provided various coordinative multi-dentate ligands and resulted in a family of metal complexes.