The synthesis and reactivity of titanium diphenyl hydrazido(2-) complexes supported by the diamido-ether ligands O(2-C6H4NSiMe 3)2 (N2ArO) and O(CH 2CH2NSiMe3)2 (N2O) are described. Reaction of Li2N2ArO or Li 2N2O with Ti(NNPh2)Cl2(py) 3 afforded Ti(N2ArO)(NNPh2)(py) 2 (14) or Ti(N2O)(NNPh2)(py)2 (15) with κ3-mer-bound diamido-ether ligands. Reaction with tBu-bipy (4,4′-di-tert-butyl-2,2′-bipyridyl) or bipy (2,2′-bipyridyl) gave a switch to κ3-fac-coordination. Reaction of 15 with Ar′NCO (Ar′ = 2,6-C6H 3iPr2) gave Ti{O(CH2CH 2NSiMe3)(CH2CH2NC(O)N(SiMe 3)Ar′)}-{N(NPh2)C(O)N(Ar′)}, in which the substrate has inserted into a Ti-Namide bond of N2O as well as adding to the Ti=Nα multiple bond. With Ar′NCS the [2+2] cycloaddition product Ti(N2O){N(NPh2) C(NAr′)S}(py) was obtained, and with Ar′NCSe a mixture was formed including Ti2(N2O)2(μ-Se)2. Both 14 and 15 reacted with ArFxCN (ArFx = C6H 3F2 or C6F5) to give Ti=N α bond insertion products of the type Ti(L){NC(Ar Fx)NNPh2}(py)2 (L = N2ArO or N2O) containing hydrazonamide ligands. Reaction of 14 with XylNC (Xyl = 2,6-C6H3Me2) gave only the isonitrile σ-adduct Ti(N2ArO)(NNPh2)(py)(CNXyl), whereas 15 underwent Nα-Nβ bond reductive cleavage with tBuNC or XylNC forming Ti(N2O)(NPh 2)(NCNtBu) or Ti{O(CH2CH2NSiMe 3)(CH2CH2NCN(SiMe3)Xyl)}(NPh 2)(NCNXyl) (27). Both contain metalated carbodiimide ligands, but in 27 an additional reaction of XylNC with the Ti-Namide bond of N 2O has taken place. Compound 15 also reacted with a number of internal alkynes RCCR′ (R = R′ = Me or Ph; R = Me, R′ = aryl) to give Nα-Nβ bond reductive cleavage products of the type Ti{O(CH2CH2NSiMe3)(CH 2CH2NC(R)C(R′)NSiMe3}(NPh2), again involving a reaction of a Ti-Namide bond. © 2013 American Chemical Society.
