A Mononuclear and High-Spin Tetrahedral TiII Complex.

Abstract

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.