A Mononuclear and High-Spin Tetrahedral TiII Complex.

A high-spin, mononuclear TiII complex, [(TptBu,Me)TiCl] [TptBu,Me- = hydridotris(3-tert-butyl-5-methylpyrazol-1-yl)borate], confined to a tetrahedral ligand-field environment, has been prepared by reduction of the precursor [(TptBu,Me)TiCl2] with KC8. Complex [(TptBu,Me)TiCl] has a 3A2 ground state (assuming C3v symmetry based on structural studies), established via a combination of high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy, solution and solid-state magnetic studies, Ti K-edge X-ray absorption spectroscopy (XAS), and both density functional theory and ab initio (complete-active-space self-consistent-field, CASSCF) calculations. The formally and physically defined TiII complex readily binds tetrahydrofuran (THF) to form the paramagnetic adduct [(TptBu,Me)TiCl(THF)], which is impervious to N2 binding. However, in the absence of THF, the TiII complex captures N2 to produce the diamagnetic complex [(TptBu,Me)TiCl]2(η1,η1;μ2-N2), with a linear Ti═N═N═Ti topology, established by single-crystal X-ray diffraction. The N2 complex was characterized using XAS as well as IR and Raman spectroscopies, thus establishing this complex to possess two TiIII centers covalently bridged by an N22- unit. A π acid such as CNAd (Ad = 1-adamantyl) coordinates to [(TptBu,Me)TiCl] without inducing spin pairing of the d electrons, thereby forming a unique high-spin and five-coordinate TiII complex, namely, [(TptBu,Me)TiCl(CNAd)]. The reducing power of the coordinatively unsaturated TiII-containing [(ΤptBu,Me)TiCl] species, quantified by electrochemistry, provides access to a family of mononuclear TiIV complexes of the type [(TptBu,Me)Ti═E(Cl)] (with E2- = NSiMe3, N2CPh2, O, and NH) by virtue of atom- or group-transfer reactions using various small molecules such as N3SiMe3, N2CPh2, N2O, and the bicyclic amine 2,3:5,6-dibenzo-7-azabicyclo[2.2.1]hepta-2,5-diene.