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

Wijeratne GB, Zolnhofer E, Fortier S, Grant LN, Carroll PJ, Chen CH, Meyer K, Krzystek J, Ozarowski A, Jackson TK, Mindiola DJ, Telser J (2015)

Publication Type: Journal article

Publication year: 2015

Journal

Inorganic Chemistry American Chemical Society

Book Volume: 54

Pages Range: 10380-10397

Journal Issue: 21

DOI: 10.1021/acs.inorgchem.5b01796

Abstract

A facile and high-yielding protocol to the known Ti(II) complex trans-[(py)4TiCl2] (py = pyridine) has been developed. Its electronic structure has been probed experimentally using magnetic susceptibility, magnetic circular dichroism, and high-frequency and high-field electron paramagnetic resonance spectroscopies in conjunction with ligand-field theory and computational methods (density functional theory and ab initio methods). These studies demonstrated that trans-[(py)4TiCl2] has a 3Eg ground state (dxy1dxz,yz1 orbital occupancy), which, as a result of spin-orbit coupling, yields a ground-state spinor doublet that is EPR active, a first excited-state doublet at ∼60 cm-1, and two next excited states at ∼120 cm-1. Reactivity studies with various unsaturated substrates are also presented in this study, which show that the Ti(II) center allows oxidative addition likely via formation of [Ti(η2-R2E2)Cl2(py)n] E = C, N intermediates. A new Ti(IV) compound, mer-[(py)3(η2-Ph2C2)TiCl2], was prepared by reaction with Ph2C2, along with the previously reported complex trans-(py)3Ti=NPh(Cl)2, from reaction with Ph2N2. Reaction with Ph2CN2 also yielded a new dinuclear Ti(IV) complex, [(py)2(Cl)2Ti(μ2:η2-N2CPh2)2Ti(Cl)2], in which the two Ti(IV) ions are inequivalently coordinated. Reaction with cyclooctatetraene (COT) yielded a new Ti(III) complex, [(py)2Ti(η8-COT)Cl], which is a rare example of a mononuclear "piano-stool" titanium complex. The complex trans-[(py)4TiCl2] has thus been shown to be synthetically accessible, have an interesting electronic structure, and be reactive toward oxidation chemistry.

Authors with CRIS profile

Eva Zolnhofer Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of Kansas (KU) US United States (USA) (US) Indiana University US United States (USA) (US) University of Pennsylvania US United States (USA) (US) Florida State University (FSU) US United States (USA) (US) Roosevelt University US United States (USA) (US)

How to cite

APA:

Wijeratne, G.B., Zolnhofer, E., Fortier, S., Grant, L.N., Carroll, P.J., Chen, C.-H.,... Telser, J. (2015). Electronic Structure and Reactivity of a Well-Defined Mononuclear Complex of Ti(II). Inorganic Chemistry, 54(21), 10380-10397. https://dx.doi.org/10.1021/acs.inorgchem.5b01796

MLA:

Wijeratne, Gayan B., et al. "Electronic Structure and Reactivity of a Well-Defined Mononuclear Complex of Ti(II)." Inorganic Chemistry 54.21 (2015): 10380-10397.

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