Imido and Amido Titanium Complexes that Contain a [OSSO]‐Type Bis(phenolato) Ligand: Synthesis, Structures, and Hydroamination Catalysis

Salt metathesis reaction of the imido complex [Ti(NR)Cl 2 (NC 5 H 5 ) 3 ] (R = t Bu, C 6 H 3 i Pr 2 ‐2,6) with 1 equiv. of the lithium salt of the corresponding [OSSO]‐type bis(phenol) [edtbpH 2 : (HOC 6 H 2 ‐ t Bu 2 ‐4,6) 2 (SCH 2 CH 2 S); rac ‐(cydtbp)H 2 : (HOC 6 H 2 ‐ t Bu 2 ‐4,6) 2 (S 2 C 6 H 10 ‐1,2)] afforded imido titanium complexes [Ti(edtbp)(N t Bu)(NC 5 H 5 )] ( 1 ), [Ti(edtbp)(NC 6 H 3 i Pr 2 ‐2,6)(NC 5 H 5 )] ( 2 ), and [Ti{ rac ‐(cydtbp)}(N t Bu)(NC 5 H 5 )] ( 3 ). The bis(dimethylamido)titanium complex [Ti(edtbp)(NMe 2 ) 2 ] ( 4 ) was synthesized by protonolysis of [Ti(NMe 2 ) 4 ] with bis(phenol) edtbpH 2 . Reaction of [Ti(NMe 2 )Cl 3 ] with the lithium salt of the bis(phenol) gave the chloro dimethylamido complex [Ti(edtbp)(NMe 2 )Cl] ( 5 ) in high yield. All complexes were characterized by NMR spectroscopy and elemental analysis. Additionally, complexes 1 and 5 were studied by X‐ray diffraction analysis. Imido titanium complex 1 shows moderate activity in the intramolecular hydroamination reaction of 5‐phenylpent‐4‐ynylamine. Complexes 1 – 3 catalyze the intramolecular hydroamination of aminoalkenes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)