Low-Coordinate and Neutral Nitrido Complexes of Vanadium

Two neutral and four-coordinate vanadium(V)-nitrido complexes have been prepared via the thermolysis of metastable vanadium(III)-azido precursors. All complexes have been fully characterized by multinuclear NMR, FT-IR, isotopic labeling, and, in most instances, single crystal X-ray diffraction. On t...

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Published inJournal of the American Chemical Society Vol. 132; no. 5; pp. 1458 - 1459
Main Authors Tran, Ba L, Pink, Maren, Gao, Xinfeng, Park, Hyunsoo, Mindiola, Daniel J
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 10.02.2010
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
OXIDE
N-N BOND
ZIRCONIUM
CHEMISTRY
HYDRAZIDE
COATINGS
LIGAND
TITANIUM
CO
ATOM
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Summary:Two neutral and four-coordinate vanadium(V)-nitrido complexes have been prepared via the thermolysis of metastable vanadium(III)-azido precursors. All complexes have been fully characterized by multinuclear NMR, FT-IR, isotopic labeling, and, in most instances, single crystal X-ray diffraction. On the basis of activation parameters, N2 extrusion to form the VN moiety is proposed to occur via an ordered and early transition state having three- or four-triazametallacycle frameworks. In addition, we demonstrate the nitrido ligand to undergo incomplete N-atom transfer to CO and CN{2,6-Me2-C6H3) to form the bent VNCX (X = O, N{2,6-Me2-C6H3}) ligands with concomitant 2e− reduction at the vanadium center.
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ISSN:0002-7863
1520-5126
DOI:10.1021/ja908303k