Unlocking CO2 Activation with A Novel Ni‐Hg‐Ni Trinuclear Complex

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.