[Ni(P Me 2N Ph 2) 2] (BF 4) 2 as an electrocatalyst for H 2 production

Stefan Wiese; Uriah J. Kilgore; Daniel L. Dubois; R. Morris Bullock

doi:10.1021/cs300019h

[Ni(P ^Me ₂N ^Ph ₂) ₂] (BF ₄) ₂ as an electrocatalyst for H ₂ production

Stefan Wiese, Uriah J. Kilgore, Daniel L. Dubois, R. Morris Bullock

Pacific Northwest National Laboratory

Research output: Contribution to journal › Article › peer-review

77 Citations (Scopus)

Abstract

A nickel(II) bis(diphosphine) complex, [Ni(P ^Me ₂N ^Ph ₂) ₂](BF ₄) ₂ (P ^Me ₂N ^Ph ₂ = 1,5-diphenyl-3,7-dimethyl- 1,5-diaza-3,7-diphosphacyclooctane), has been synthesized and characterized. This complex, which contains pendant amines in the diphosphine ligand, is an electrocatalyst for hydrogen production by proton reduction. Using [(DMF)H]OTf as the acid, a turnover frequency of 1,540 s ^-1 was obtained with no added water, and a turnover frequency of 6,700 s ^-1 was found with 1.0 M water added. Thermochemical studies show that the hydride donor ability of [HNi(P ^Me ₂N ^Ph ₂) ₂](BF ₄) is δG° _H- = 54.0 kcal/mol, and we estimate a driving force for H ₂ elimination of 13.8 kcal/mol. [Ni(P ^Me ₂N ^Ph ₂) ₂](BF ₄) ₂ is the fastest H ₂ production catalyst in the [Ni(P ^R ₂N ^R' ₂) ₂] (BF ₄) ₂ family of complexes.

Original language	English
Pages (from-to)	720-727
Number of pages	8
Journal	ACS Catalysis
Volume	2
Issue number	5
DOIs	https://doi.org/10.1021/cs300019h
Publication status	Published - May 4 2012

Keywords

electrocatalysis
hydrogen
nickel
pendant amine
proton reduction
proton relay

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1021/cs300019h

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@article{e578e8da83684c18a22a308f380e7ee7,

title = "[Ni(P Me 2N Ph 2) 2] (BF 4) 2 as an electrocatalyst for H 2 production",

abstract = "A nickel(II) bis(diphosphine) complex, [Ni(P Me 2N Ph 2) 2](BF 4) 2 (P Me 2N Ph 2 = 1,5-diphenyl-3,7-dimethyl- 1,5-diaza-3,7-diphosphacyclooctane), has been synthesized and characterized. This complex, which contains pendant amines in the diphosphine ligand, is an electrocatalyst for hydrogen production by proton reduction. Using [(DMF)H]OTf as the acid, a turnover frequency of 1,540 s -1 was obtained with no added water, and a turnover frequency of 6,700 s -1 was found with 1.0 M water added. Thermochemical studies show that the hydride donor ability of [HNi(P Me 2N Ph 2) 2](BF 4) is δG° H- = 54.0 kcal/mol, and we estimate a driving force for H 2 elimination of 13.8 kcal/mol. [Ni(P Me 2N Ph 2) 2](BF 4) 2 is the fastest H 2 production catalyst in the [Ni(P R 2N R' 2) 2] (BF 4) 2 family of complexes.",

keywords = "electrocatalysis, hydrogen, nickel, pendant amine, proton reduction, proton relay",

author = "Stefan Wiese and Kilgore, {Uriah J.} and Dubois, {Daniel L.} and Bullock, {R. Morris}",

year = "2012",

month = may,

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doi = "10.1021/cs300019h",

language = "English",

volume = "2",

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TY - JOUR

T1 - [Ni(P Me 2N Ph 2) 2] (BF 4) 2 as an electrocatalyst for H 2 production

AU - Wiese, Stefan

AU - Kilgore, Uriah J.

AU - Dubois, Daniel L.

AU - Bullock, R. Morris

PY - 2012/5/4

Y1 - 2012/5/4

N2 - A nickel(II) bis(diphosphine) complex, [Ni(P Me 2N Ph 2) 2](BF 4) 2 (P Me 2N Ph 2 = 1,5-diphenyl-3,7-dimethyl- 1,5-diaza-3,7-diphosphacyclooctane), has been synthesized and characterized. This complex, which contains pendant amines in the diphosphine ligand, is an electrocatalyst for hydrogen production by proton reduction. Using [(DMF)H]OTf as the acid, a turnover frequency of 1,540 s -1 was obtained with no added water, and a turnover frequency of 6,700 s -1 was found with 1.0 M water added. Thermochemical studies show that the hydride donor ability of [HNi(P Me 2N Ph 2) 2](BF 4) is δG° H- = 54.0 kcal/mol, and we estimate a driving force for H 2 elimination of 13.8 kcal/mol. [Ni(P Me 2N Ph 2) 2](BF 4) 2 is the fastest H 2 production catalyst in the [Ni(P R 2N R' 2) 2] (BF 4) 2 family of complexes.

AB - A nickel(II) bis(diphosphine) complex, [Ni(P Me 2N Ph 2) 2](BF 4) 2 (P Me 2N Ph 2 = 1,5-diphenyl-3,7-dimethyl- 1,5-diaza-3,7-diphosphacyclooctane), has been synthesized and characterized. This complex, which contains pendant amines in the diphosphine ligand, is an electrocatalyst for hydrogen production by proton reduction. Using [(DMF)H]OTf as the acid, a turnover frequency of 1,540 s -1 was obtained with no added water, and a turnover frequency of 6,700 s -1 was found with 1.0 M water added. Thermochemical studies show that the hydride donor ability of [HNi(P Me 2N Ph 2) 2](BF 4) is δG° H- = 54.0 kcal/mol, and we estimate a driving force for H 2 elimination of 13.8 kcal/mol. [Ni(P Me 2N Ph 2) 2](BF 4) 2 is the fastest H 2 production catalyst in the [Ni(P R 2N R' 2) 2] (BF 4) 2 family of complexes.

KW - electrocatalysis

KW - hydrogen

KW - nickel

KW - pendant amine

KW - proton reduction

KW - proton relay

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