Tale of Three Molecular Nitrides: Mononuclear Vanadium (V) and (IV) Nitrides As Well As a Mixed-Valence Trivanadium Nitride Having a V3N4Double-Diamond Core

G. Jafari M, Fehn D, Reinholdt A, Hernández-Prieto C, Patel P, Gau MR, Carroll PJ, Krzystek J, Liu C, Ozarowski A, Telser J, Delferro M, Meyer K, Mindiola DJ (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Journal of the American Chemical Society American Chemical Society

DOI: 10.1021/jacs.2c00276

Abstract

Transmetallation of [VCl3(THF)3] and [TlTptBu,Me] afforded [(TptBu,Me)VCl2] (1, TptBu,Me = hydro-tris(3-tert-butyl-5-methylpyrazol-1-yl)borate), which was reduced with KC8 to form a C3v symmetric VII complex, [(TptBu,Me)VCl] (2). Complex 1 has a high-spin (S = 1) ground state and displays rhombic high-frequency and -field electron paramagnetic resonance (HFEPR) spectra, while complex 2 has an S = 3/2 4A2 ground state observable by conventional EPR spectroscopy. Complex 1 reacts with NaN3 to form the VV nitride-azide complex [(TptBu,Me)VN(N3)] (3). A likely VIII azide intermediate en route to 3, [(TptBu,Me)VCl(N3)] (4), was isolated by reacting 1 with N3SiMe3. Complex 4 is thermally stable but reacts with NaN3 to form 3, implying a bis-azide intermediate, [(TptBu,Me)V(N3)2] (A), leading to 3. Reduction of 3 with KC8 furnishes a trinuclear and mixed-valent nitride, [{(TptBu,Me)V}2(μ4-VN4)] (5), conforming to a Robin-Day class I description. Complex 5 features a central vanadium ion supported only by bridging nitride ligands. Contrary to 1, complex 2 reacts with NaN3 to produce an azide-bridged dimer, [{(TptBu,Me)V}2(1,3-μ2-N3)2] (6), with two antiferromagnetically coupled high-spin VII ions. Complex 5 could be independently produced along with [(κ2-TptBu,Me)2V] upon photolysis of 6 in arene solvents. The putative {VIVN} intermediate, [(TptBu,Me)VN] (B), was intercepted by photolyzing 6 in a coordinating solvent, such as tetrahydrofuran (THF), yielding [(TptBu,Me)VN(THF)] (B-THF). In arene solvents, B-THF expels THF to afford 5 and [(κ2-TptBu,Me)2V]. A more stable adduct (B-OPPh3) was prepared by reacting B-THF with OPPh3. These adducts of B are the first neutral and mononuclear VIV nitride complexes to be isolated.

Authors with CRIS profile

Dominik Fehn Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of Pennsylvania US United States (USA) (US) Argonne National Laboratory 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:

G. Jafari, M., Fehn, D., Reinholdt, A., Hernández-Prieto, C., Patel, P., Gau, M.R.,... Mindiola, D.J. (2022). Tale of Three Molecular Nitrides: Mononuclear Vanadium (V) and (IV) Nitrides As Well As a Mixed-Valence Trivanadium Nitride Having a V3N4Double-Diamond Core. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.2c00276

MLA:

G. Jafari, Mehrafshan, et al. "Tale of Three Molecular Nitrides: Mononuclear Vanadium (V) and (IV) Nitrides As Well As a Mixed-Valence Trivanadium Nitride Having a V3N4Double-Diamond Core." Journal of the American Chemical Society (2022).

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