Vanadium: Organometallic ChemistryBased in part on the article Vanadium: Organometallic Chemistry by Dieter Rehder which appeared in the<i>Encyclopedia of Inorganic Chemistry, First Edition</i>.

Hirao, Toshikazu

doi:10.1002/0470862106.ia254

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“…To achieve higher oxidation states, we thus considered V, which has applications in heterogeneous catalysis, 2,10 including for selective alkane oxidation, 11 and in homogeneous catalysis 12,13 and is a stronger reducing agent than Pt. Also, V is known to be able to access a greater variety of oxidation states (−3 to +5) 14 although none of these have been previously characterized in an on-surface environment for metal−ligand systems; only various VO x surfaces have been characterized in surface studies. 15…”

Section: ■ Introductionmentioning

confidence: 99%

Two- and Three-Electron Oxidation of Single-Site Vanadium Centers at Surfaces by Ligand Design

et al. 2015

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Rational, systematic tuning of single-site metal centers on surfaces offers a new approach to increase selectivity in heterogeneous catalysis reactions. Although such metal centers of uniform oxidation states have been achieved, the ability to control their oxidation states through the use of carefully designed ligands had not been shown. To this end, tetrazine ligands functionalized by two pyridinyl or pyrimidinyl substituents were deposited, along with vanadium metal, on the Au(100) surface. The greater oxidizing power of the bis-pyrimidinyltetrazine facilitates the on-surface redox formation of V(3+), compared to V(2+) when paired with the bis-pyridinyltetrazine, as determined by X-ray photoelectron spectroscopy. This demonstrates the ability to control metal oxidation states in surface coordination architectures by altering the redox properties of organic ligands. The metal-ligand complexes take the form of one-dimensional polymeric chains, resolved by scanning tunneling microscopy. The chain structures in the first layer are very uniform and are based on the same quasi-square-planar coordination geometry around single-site V with either ligand. Formation of a different, dimer structure is observed in the early stages of the second layer formation. These systems offer new opportunities in controlling the oxidation state of single-site transition metal atoms at a surface for new advances in heterogeneous catalysts.

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Section: ■ Introductionmentioning

confidence: 99%

Two- and Three-Electron Oxidation of Single-Site Vanadium Centers at Surfaces by Ligand Design

et al. 2015

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Vanadium: Organometallic ChemistryBased in part on the article Vanadium: Organometallic Chemistry by Dieter Rehder which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Abstract: This review surveys the chemistry of organovanadium compounds. Their syntheses and reactivities are described depending on the coordination‐binding mode.

Cited by 1 publication

References 169 publications

Two- and Three-Electron Oxidation of Single-Site Vanadium Centers at Surfaces by Ligand Design

Two- and Three-Electron Oxidation of Single-Site Vanadium Centers at Surfaces by Ligand Design

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