Volume 137, Issue 8 e202420391
Forschungsartikel

Unlocking CO2 Activation With a Novel Ni−Hg−Ni Trinuclear Complex

Dr. Naser Rahimi

Dr. Naser Rahimi

Département de chimie, Université de Montréal, Montréal, Québec, Canada, H3C 3J7

Contribution: Conceptualization (equal), Formal analysis (equal), ​Investigation (equal), Methodology (equal), Writing - review & editing (equal)

Search for more papers by this author
Dr. Christine Lepetit

Dr. Christine Lepetit

LCC–CNRS, Université de Toulouse, CNRS, Toulouse, France

Contribution: Data curation (lead), Formal analysis (lead), Methodology (lead), Writing - review & editing (supporting)

Search for more papers by this author
Prof. Davit Zargarian

Corresponding Author

Prof. Davit Zargarian

Département de chimie, Université de Montréal, Montréal, Québec, Canada, H3C 3J7

Contribution: Conceptualization (lead), Formal analysis (lead), Funding acquisition (lead), ​Investigation (lead), Project administration (lead), Supervision (lead), Validation (lead), Writing - original draft (lead)

Search for more papers by this author
First published: 07 January 2025

Abstract

Compounds featuring bonds between mercury and transition metals are of interest for their intriguing/ambiguous bonding and scarcely explored reactivities. We report herein the synthesis and reactivities of the new compound [(POCOP)Ni]2Hg, [Ni2Hg], featuring a trinuclear Ni−Hg−Ni core (POCOP=κP,κC,κP'-2,6-(i-Pr2PO)2C6H3). [Ni2Hg] reacts with CO2 to give the carbonate-bridged complex [Ni2CO3]. Bubbling CO gas through a solution of [Ni2CO3] gave its μ-CO2 analogue [Ni2CO2], which itself reacts with CO2 to give back [Ni2CO3], indicating that these two compounds interconvert reversibly. This implies that the formation of [Ni2CO3] from [Ni2Hg] and CO2 constitutes a reductive disproportionation of two molecules of CO2 into CO32− and CO. Tests showed that this process proceeds through three steps, an initial CO2 insertion to give [Ni2CO2], followed by another CO2 insertion to give the second intermediate [Ni2C2O4], and the latter's decarbonylation to give [Ni2CO3]. Although the putative second intermediate could not be isolated, we have shown that it likely features a μ-carbonyl-carbonate rather than a μ-oxalate moiety, because the latter complex is thermally stable to decarbonylation. Reduction of [Ni2CO3] with excess Na/Hg regenerates [Ni2Hg], establishing that the observed deoxygenation of CO2 in this system can, in principle, be catalytic in the presence of excess reductant.

Conflict of Interests

The authors declare no conflict of interest.

Data Availability Statement

The data that support the findings of this study are available in the supplementary material of this article.

The full text of this article hosted at iucr.org is unavailable due to technical difficulties.