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 language | English |
|---|---|
| Pages (from-to) | 14244-14250 |
| Number of pages | 7 |
| Journal | Journal of the American Chemical Society |
| Volume | 139 |
| Issue number | 40 |
| DOIs | |
| Publication status | Published - Oct 11 2017 |
Fingerprint
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 journal › Article
}
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 -