Thermodynamic and Structural Factors That Influence the Redox Potentials of Tungsten–Alkylidyne Complexes

Rudshteyn, Benjamin; Vibbert, Hunter B.; May, Richard; Wasserman, Eric; Warnke, Ingolf; Hopkins, Michael D.; Batista, Victor S.

doi:10.1021/acscatal.7b01636

Thermodynamic and Structural Factors That Influence the Redox Potentials of Tungsten–Alkylidyne Complexes

Journal Article · Fri Jul 14 00:00:00 EDT 2017 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b01636· OSTI ID:1485312

^[1]; ^[2]; May, Richard ^[1]; Wasserman, Eric ^[1]; Warnke, Ingolf ^[1]; ^[2]; ^[1]

Yale Univ., New Haven, CT (United States)
Univ. of Chicago, IL (United States)

The thermodynamic and structural factors that influence the redox properties of an extensive set of tungsten–alkylidyne complexes (W(CR)L₄X) are assessed by combining synthesis, electrochemistry, and computational modeling based on free energy calculations of oxidation potentials at the density functional theory level. The observed linear correlations among oxidation potentials, HOMO energies, and gas-phase ionization energies are found to be consistent with the approximately constant solvation free energy differences between reduced and oxidized species over the complete set. The W–X bond length, trans to the alkylidyne ligand, is discovered to be a good descriptor of the positioning of the key frontier orbitals that regulate the redox properties of the complexes.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: Air Force Office of Scientific Research (AFOSR); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-07ER15910

OSTI ID:: 1485312

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 9 Vol. 7; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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