Electronic Structure and Reactivity of a Well-Defined Mononuclear Complex of Ti(II).

摘要: A facile and high-yielding protocol to the known Ti(II) complex trans-[(py)4TiCl2] (py = pyridine) has been developed. Its electronic structure probed experimentally using magnetic susceptibility, circular dichroism, high-frequency high-field electron paramagnetic resonance spectroscopies in conjunction with ligand-field theory computational methods (density functional ab initio methods). These studies demonstrated that a 3Eg ground state (dxy1dxz,yz1 orbital occupancy), which, as result of spin–orbit coupling, yields ground-state spinor doublet is EPR active, first excited-state at ∼60 cm–1, two next excited states ∼120 cm–1. Reactivity various unsaturated substrates are also presented this study, which show center allows oxidative addition likely via formation [Ti(η2-R2E2)Cl2(py)n] E C, N intermediates. new Ti(IV) compound, mer-[(py)3(η2-Ph2C2)TiCl2], was prepared by reaction ...