A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride

Ryan C. Cammarota, Matthew V. Vollmer, Jing Xie, Jingyun Ye, John Linehan, Samantha A. Burgess, Aaron Appel, Laura Gagliardi, Connie C. Lu

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→ Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centered catalysts. The Lewis acidic Ga(III) ion plays a pivotal role in stabilizing catalytic intermediates, including a rare anionic d10 Ni hydride. Structural and in situ characterization of this reactive intermediate support a terminal Ni-H moiety, for which the thermodynamic hydride donor strength rivals those of precious metal hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis.

Original languageEnglish
Pages (from-to)14244-14250
Number of pages7
JournalJournal of the American Chemical Society
Volume139
Issue number40
DOIs
Publication statusPublished - Oct 11 2017

Fingerprint

Gallium
Hydrogenation
Nickel
Hydrides
formic acid
Metals
Precious metals
Catalysts
Catalysis
Transition metals
Catalyst activity
Earth (planet)
Thermodynamics
Ions
Hydrogen
Temperature

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride. / Cammarota, Ryan C.; Vollmer, Matthew V.; Xie, Jing; Ye, Jingyun; Linehan, John; Burgess, Samantha A.; Appel, Aaron; Gagliardi, Laura; Lu, Connie C.

In: Journal of the American Chemical Society, Vol. 139, No. 40, 11.10.2017, p. 14244-14250.

Research output: Contribution to journalArticle

Cammarota, Ryan C. ; Vollmer, Matthew V. ; Xie, Jing ; Ye, Jingyun ; Linehan, John ; Burgess, Samantha A. ; Appel, Aaron ; Gagliardi, Laura ; Lu, Connie C. / A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 40. pp. 14244-14250.
@article{17d06c34056444d3a1f8c7a2a33f2107,
title = "A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride",
abstract = "Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→ Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centered catalysts. The Lewis acidic Ga(III) ion plays a pivotal role in stabilizing catalytic intermediates, including a rare anionic d10 Ni hydride. Structural and in situ characterization of this reactive intermediate support a terminal Ni-H moiety, for which the thermodynamic hydride donor strength rivals those of precious metal hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis.",
author = "Cammarota, {Ryan C.} and Vollmer, {Matthew V.} and Jing Xie and Jingyun Ye and John Linehan and Burgess, {Samantha A.} and Aaron Appel and Laura Gagliardi and Lu, {Connie C.}",
year = "2017",
month = "10",
day = "11",
doi = "10.1021/jacs.7b07911",
language = "English",
volume = "139",
pages = "14244--14250",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "40",

}

TY - JOUR

T1 - A Bimetallic Nickel-Gallium Complex Catalyzes CO2 Hydrogenation via the Intermediacy of an Anionic d10 Nickel Hydride

AU - Cammarota, Ryan C.

AU - Vollmer, Matthew V.

AU - Xie, Jing

AU - Ye, Jingyun

AU - Linehan, John

AU - Burgess, Samantha A.

AU - Appel, Aaron

AU - Gagliardi, Laura

AU - Lu, Connie C.

PY - 2017/10/11

Y1 - 2017/10/11

N2 - Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→ Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centered catalysts. The Lewis acidic Ga(III) ion plays a pivotal role in stabilizing catalytic intermediates, including a rare anionic d10 Ni hydride. Structural and in situ characterization of this reactive intermediate support a terminal Ni-H moiety, for which the thermodynamic hydride donor strength rivals those of precious metal hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis.

AB - Large-scale CO2 hydrogenation could offer a renewable stream of industrially important C1 chemicals while reducing CO2 emissions. Critical to this opportunity is the requirement for inexpensive catalysts based on earth-abundant metals instead of precious metals. We report a nickel-gallium complex featuring a Ni(0)→ Ga(III) bond that shows remarkable catalytic activity for hydrogenating CO2 to formate at ambient temperature (3150 turnovers, turnover frequency = 9700 h-1), compared with prior homogeneous Ni-centered catalysts. The Lewis acidic Ga(III) ion plays a pivotal role in stabilizing catalytic intermediates, including a rare anionic d10 Ni hydride. Structural and in situ characterization of this reactive intermediate support a terminal Ni-H moiety, for which the thermodynamic hydride donor strength rivals those of precious metal hydrides. Collectively, our experimental and computational results demonstrate that modulating a transition metal center via a direct interaction with a Lewis acidic support can be a powerful strategy for promoting new reactivity paradigms in base-metal catalysis.

UR - http://www.scopus.com/inward/record.url?scp=85031112400&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85031112400&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b07911

DO - 10.1021/jacs.7b07911

M3 - Article

VL - 139

SP - 14244

EP - 14250

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 40

ER -