Formation and reactivity of the terminal vanadium nitride functionality

Tran BL, Krzystek J, Ozarowski A, Chen CH, Pink M, Karty JA, Telser J, Meyer K, Mindiola DJ (2013)

Publication Type: Journal article, Original article

Publication year: 2013

Journal

European Journal of Inorganic Chemistry Wiley-VCH Verlag

Original Authors: Tran B.L., Krzystek J., Ozarowski A., Chen C.-H., Pink M., Karty J.A., Telser J., Meyer K., Mindiola D.J.

Publisher: Wiley-VCH Verlag

Pages Range: 3916-3929

DOI: 10.1002/ejic.201300178

Abstract

The transformation of vanadium(III) azides, [(nacnac)V(N )-(X)] {nacnac = [ArNC(CH)] CH, Ar = 2,6-(CHMe)C H; X = Ntol, where tol = 4-MeCH, n = 1; X = ArO, n = 2}, to their corresponding vanadium(V) nitrides, [(nacnac)-V=N(X)], was investigated through an isotopic labeling crossover experiment. The nuclearity of the azide species is dependent on the size of the supporting ligand, X, with X = ArO, thus featuring a VN core with two μ-1,3- N bridging ligands across the VIII centers. SQUID magnetization studies and multifrequency, high-field EPR (HFEPR) experiments reveal the mononuclear azide complex to be consistent with an S = 1 system, while the dimeric azide system is weakly antiferromagnetically coupled with a spin singlet ground state and thermally accessible triplet and quintet states. These combined results suggest that the transformation of a vanadium(III) azide to a vanadium(V) nitride most likely occurs by a bimetallic mechanism, where Lewis bases inhibit N extrusion. Room-temperature generation of the nitride products from their corresponding azides can also be accomplished stoichiometrically with a Lewis acid, such as B(CF) , and catalytically, through an unsaturated vanadium(II) fragment, [(nacnac)V(Ntol)]. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Authors with CRIS profile

Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

Indiana University US United States (USA) (US) Roosevelt University US United States (USA) (US) Florida State University (FSU) US United States (USA) (US)

How to cite

APA:

Tran, B.L., Krzystek, J., Ozarowski, A., Chen, C.-H., Pink, M., Karty, J.A.,... Mindiola, D.J. (2013). Formation and reactivity of the terminal vanadium nitride functionality. European Journal of Inorganic Chemistry, 3916-3929. https://dx.doi.org/10.1002/ejic.201300178

MLA:

Tran, Ba L., et al. "Formation and reactivity of the terminal vanadium nitride functionality." European Journal of Inorganic Chemistry (2013): 3916-3929.

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