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Xue L, Ahlquist MS. A DFT study: why do [Ni(P(R)(2)N(R')2)2]2+ complexes facilitate the electrocatalytic oxidation of formate?. Inorg Chem. 2014;53(7):3281-9doi: 10.1021/ic4027317.
Xue, L., & Ahlquist, M. S. (2014). A DFT study: why do [Ni(P(R)(2)N(R')2)2]2+ complexes facilitate the electrocatalytic oxidation of formate?. Inorganic chemistry, 53(7), 3281-9. https://doi.org/10.1021/ic4027317
Xue, Liqin, and Ahlquist, Mårten S G. "A DFT study: why do [Ni(P(R)(2)N(R')2)2]2+ complexes facilitate the electrocatalytic oxidation of formate?." Inorganic chemistry vol. 53,7 (2014): 3281-9. doi: https://doi.org/10.1021/ic4027317
Xue L, Ahlquist MS. A DFT study: why do [Ni(P(R)(2)N(R')2)2]2+ complexes facilitate the electrocatalytic oxidation of formate?. Inorg Chem. 2014 Apr 07;53(7):3281-9. doi: 10.1021/ic4027317. Epub 2014 Mar 18. PMID: 24635499.
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Inorg Chem. 2014 Apr 07;53(7):3281-9. doi: 10.1021/ic4027317. Epub 2014 Mar 18.

A DFT study: why do [Ni(P(R)(2)N(R')2)2]2+ complexes facilitate the electrocatalytic oxidation of formate?.

Inorganic chemistry

Liqin Xue, Mårten S G Ahlquist

Affiliations

  1. Division of Theoretical Chemistry & Biology, School of Biotechnology, KTH Royal Institute of Technology , SE-10691 Stockholm, Sweden.

PMID: 24635499 DOI: 10.1021/ic4027317

Abstract

We present a DFT study of the reaction mechanism on electrocatalytic oxidation of formate by a family of [Ni(P(R)2N(R('))2)2](2+) complexes (P(R)2N(R('))2 = 1,5-diR'-3,7-diR derivative of 1,5-diaza-3,7-diphosphacyclooctane, where R and R' are aryl or alkyl groups). [Ni(P(Ph)2N(Me)2)2](2+) complex 1 was used as a model complex to mimic a family of [Ni(P(R)2N(R('))2)2](2+) complexes. Our calculated results show that the decarboxylation step (corresponding to TS3) is the rate-determining step for the electrocatalytic oxidation of formate and that a Ni(II)-H intermediate is involved in the reaction mechanism. The pendant amine plays an important role in the deprotonation of the nickel hydride complex generated in the decarboxylation step. In addition, our study indicates that the choice of external bases is important for removing the proton (H(+)) from the nitrogen-protonated nickel(0) complexes. For the electrocatalytic oxidation of formate using the catalytically inactive [Ni(depe)2](2+) (depe = 1,2-bis(diethylphosphino)ethane) complex, calculations on 1-depe have also been carried out for comparison.

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