Catalytic Applications of Vanadium: A Mechanistic Perspective

Abstract

The chemistry of vanadium has seen remarkable activity in the past 50 years. In the present review, reactions catalyzed by homogeneous and supported vanadium complexes from 2008 to 2018 are summarized and discussed. Particular attention is given to mechanistic and kinetics studies of vanadium-catalyzed reactions including oxidations of alkanes, alkenes, arenes, alcohols, aldehydes, ketones, and sulfur species, as well as oxidative C–C and C–O bond cleavage, carbon–carbon bond formation, deoxydehydration, haloperoxidase, cyanation, hydrogenation, dehydrogenation, ring-opening metathesis polymerization, and oxo/imido heterometathesis. Additionally, insights into heterogeneous vanadium catalysis are provided when parallels can be drawn from the homogeneous literature.

Oxidative Dehydrogenation of Propane over Vanadium-Containing Faujasite Zeolite

“…Other advantages of the ODH reaction include its exothermicity, lower operation temperatures, and minimization of the carbon deposit due to the oxidizing conditions [3]. The main shortcoming of the ODH process, however, is a parallel deep oxidation of the substrates and products [4][5][6][7][8][9]. There are also secondary problems, such as the removal of the reaction heat, flammability of the reaction mixture, and the possibility of the reaction runaway.…”

“…The literature reviews the current status of the research in the selective oxidation of light hydrocarbons [2,[4][5][6][7][8][9]. The commonly used catalysts for the oxidative dehydrogenation of lower alkanes include vanadium-based systems [8][9][10], V-Mg-O systems [11][12][13], molybdate systems [14,15], rare earth metal systems [8], phosphate systems [16,17], and boron nitride systems [18]. An important factor in the design of efficient catalysts for alkane ODH is the isolation of the active sites [2,19].…”

New Complex of Copper on Boehmite Nanoparticles as Highly Efficient and Reusable Nanocatalyst for Synthesis of Sulfides and Ethers

“…Recently, solid materials (especially nanoparticles) were applied as support in catalysis science toward doing reaction under green chemistry conditions . Various solid materials or different nanoparticles were applied as support.…”

Titanium and Vanadium Catalysts with 2-Hydroxyphenyloxazoline and Oxazine Ligands for Ethylene-Norbornene (co)Polymerization

“…Similar to the synthesis of polyethylene and ethylene copolymers with 1-olefins, in particular E-NB copolymers, the catalysts with zirconium [1,6,12,19] and titanium [8,12,20] atoms in the active center are the most often studied. The vanadium catalysts [21,22] are less studied, but they receive interest because it is possible to obtain the E-NB copolymers with high molecular weight, narrow molecular weight distribution, and high norbornene incorporation [13,[15][16][17][18][23][24][25][26]. In contrast to the zirconium and titanium catalysts, which work best after methylaluminoxane (MAO) activation [1,[6][7][8]12,19,20], the vanadium catalysts reveal the best performance when activated by AlEt 2 Cl in the presence of reactivator, ethyl trichloroacetate (ETA), which prevents reduction of the vanadium atom to lower oxidation states and influences positively termination and re-initiation processes [13][14][15][16][17][18].…”

“…In contrast to the zirconium and titanium catalysts, which work best after methylaluminoxane (MAO) activation [1,[6][7][8]12,19,20], the vanadium catalysts reveal the best performance when activated by AlEt2Cl in the presence of reactivator, ethyl trichloroacetate (ETA), which prevents reduction of the vanadium atom to lower oxidation states and influences positively termination and re-initiation processes [13][14][15][16][17][18]. A method of stabilizing the vanadium active center, and in consequence, a prolongation of catalyst lifetime, is to apply ligands with electron-donating atoms-oxygen, nitrogen, or phosphorus [14][15][16][17][18][20][21][22][23][24][25][26][27][28]. Heterocyclic compounds like 4,5-dihydro-1,3-oxazole (oxazoline) derivatives seem to meet this requirement.…”