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Title: Antimony Complexes for Electrocatalysis: Activity of a Main-Group Element in Proton Reduction

Authors:
 [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, Yale University, New Haven CT 06520 USA, Energy Sciences Institute, Yale University, West Haven CT 06516 USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1374917
Grant/Contract Number:
FG02-07ER15909
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 129; Journal Issue: 31; Related Information: CHORUS Timestamp: 2017-11-10 06:49:49; Journal ID: ISSN 0044-8249
Publisher:
German Chemical Society
Country of Publication:
Germany
Language:
English

Citation Formats

Jiang, Jianbing, Materna, Kelly L., Hedström, Svante, Yang, Ke R., Crabtree, Robert H., Batista, Victor S., and Brudvig, Gary W. Antimony Complexes for Electrocatalysis: Activity of a Main-Group Element in Proton Reduction. Germany: N. p., 2017. Web. doi:10.1002/ange.201704700.
Jiang, Jianbing, Materna, Kelly L., Hedström, Svante, Yang, Ke R., Crabtree, Robert H., Batista, Victor S., & Brudvig, Gary W. Antimony Complexes for Electrocatalysis: Activity of a Main-Group Element in Proton Reduction. Germany. doi:10.1002/ange.201704700.
Jiang, Jianbing, Materna, Kelly L., Hedström, Svante, Yang, Ke R., Crabtree, Robert H., Batista, Victor S., and Brudvig, Gary W. 2017. "Antimony Complexes for Electrocatalysis: Activity of a Main-Group Element in Proton Reduction". Germany. doi:10.1002/ange.201704700.
@article{osti_1374917,
title = {Antimony Complexes for Electrocatalysis: Activity of a Main-Group Element in Proton Reduction},
author = {Jiang, Jianbing and Materna, Kelly L. and Hedström, Svante and Yang, Ke R. and Crabtree, Robert H. and Batista, Victor S. and Brudvig, Gary W.},
abstractNote = {},
doi = {10.1002/ange.201704700},
journal = {Angewandte Chemie},
number = 31,
volume = 129,
place = {Germany},
year = 2017,
month = 6
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on July 4, 2018
Publisher's Accepted Manuscript

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  • A variety of supported catalysts were prepared by the chemical deposition of Pt and Pt-Ru particles on chemically prepared poly(3,4-ethylenedioxythiophene)/poly(styrene-4-sulfonate) (PEDOT/PSS) and PEDOT/polyvinylsulfate (PVS) composites. The polymer particles were designed to provide a porous, proton-conducting and electron-conducting catalyst support for use in fuel cells. These polymer-supported catalysts were characterized by electron microscopy, impedance spectroscopy, cyclic voltammetry, and conductivity measurements. Their catalytic activities toward hydrogen and methanol oxidation and oxygen reduction were evaluated in proton exchange membrane fuel-cell-type gas diffusion electrodes. Activities for oxygen reduction comparable to that obtained with a commercial carbon-supported catalyst were observed, whereas those for hydrogen andmore » methanol oxidation were significantly inferior, although still high for prototype catalysts.« less
  • Formyl complexes, MCHO, of first- and second-row metals and metal hydrides (M = Li, BeH, BH/sub 2/, Na, MgH, AlH/sub 2/) have been investigated by means of ab initio calculations (MP2/6-31+G*//6-31G* and lower levels). Both eta/sup 2/ (i.e., bridged) and eta/sup 1/ coordination of the metals are found: the former is favored by larger electronegativity differences between the metal and the formyl carbon. Such eta/sup 2/ coordination is characterized by rather long CO bonds, significant alkoxy-carbene character in the formyl group, and a bridging energy of about 5-8 kcal/mol for M = BeH and AlH/sub 2/. The formyl carbon-metal interactionsmore » are predominantly ionic. The insertion reaction of CO into the LiH bond, a model for similar processes in transition-metal compounds, proceeds via an initially formed linear coordination complex, HLi-CO, and a three-membered ring transition structure.d The latter lies energetically about 19 kcal/mol above the complex. The overall activation and reaction energies from LiH + CO to the formyllithium product, LiCHO, are +13 and -3 kcal/mol, respectively. The energies of the reaction of the other metal hydrides with CO to form the corresponding formyl compounds are all endothermic by about 1-7 kcal/mol. Thus, with the exception of M = Li, all the formyl complexes, MCHO, are thermodynamically unstable, but they may be observable at lower temperatures if the activation energies for the loss of CO are comparable to that of LiCHO (about 16 kcal/mol).« less
  • Abstract not provided.
  • The synthesis of the rhenium/main-group-metal bridging CO/sub 2/ or carboxylate complexes of the formula (eta/sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(CO/sub 2/ML/sub n/) where M = Li, K, Ge, Sn, or Pb from the rhenium carboxylic acid (eta/sup 5/-C/sub 5/H/sub 5/)Re(NO)(PPh/sub 3/)(COOH) is reported. The molecular structure of the complexes was investigated, and both monodentate and bidentate carboxylate binding modes were observed with the symmetrical bidentate binding in the tin complex being unprecedented. Clean thermal decarboxylation occurs when the main-group metal is tin or lead to provide a convenient route to the preparation of heterobimetallic complexes. 14 references, 1 figure.