5 research outputs found
Reduction of CO\u3csub\u3e2\u3c/sub\u3e By a Masked Two-Coordinate Cobalt(I) Complex and Characterization of a Proposed Oxodicobalt(II) Intermediate
Fixation and chemical reduction of CO2 are important for utilization of this abundant resource, and understanding the detailed mechanism of C-O cleavage is needed for rational development of CO2 reduction methods. Here, we describe a detailed analysis of the mechanism of the reaction of a masked two-coordinate cobalt(i) complex, LtBuCo (where LtBu = 2,2,6,6-tetramethyl-3,5-bis[(2,6-diisopropylphenyl)imino]hept-4-yl), with CO2, which yields two products of C-O cleavage, the cobalt(i) monocarbonyl complex LtBuCo(CO) and the dicobalt(ii) carbonate complex (LtBuCo)2(Ī¼-CO3). Kinetic studies and computations show that the ĪŗN,Ī·6-arene isomer of LtBuCo rearranges to the Īŗ2N,Nā² binding mode prior to binding of CO2, which contrasts with the mechanism of binding of other substrates to LtBuCo. Density functional theory (DFT) studies show that the only low-energy pathways for cleavage of CO2 proceed through bimetallic mechanisms, and DFT and highly correlated domain-based local pair natural orbital coupled cluster (DLPNO-CCSD(T)) calculations reveal the cooperative effects of the two metal centers during facile C-O bond rupture. A plausible intermediate in the reaction of CO2 with LtBuCo is the oxodicobalt(II) complex LtBuCoOCoLtBu, which has been independently synthesized through the reaction of LtBuCo with N2O. The rapid reaction of LtBuCoOCoLtBu with CO2 to form the carbonate product indicates that the oxo species is kinetically competent to be an intermediate during CO2 cleavage by LtBuCo. LtBuCoOCoLtBu is a novel example of a thoroughly characterized molecular cobalt-oxo complex where the cobalt ions are clearly in the +2 oxidation state. Its nucleophilic reactivity is a consequence of high charge localization on the Ī¼-oxo ligand between two antiferromagnetically coupled high-spin cobalt(ii) centers, as characterized by DFT and multireference complete active space self-consistent field (CASSCF) calculations
Spin Isomers and Ligand Isomerization in a Three-Coordinate Cobalt(I) Carbonyl Complex
Hemilabile ligands, which have one donor that can reversibly bind to a metal, are widely used in transition-metal catalysts to create open coordination sites. This change in coordination at the metal can also cause spin-state changes. Here, we explore a cobalt(I) system that is poised on the brink of hemilability and of a spin-state change and can rapidly interconvert between different spin states with different structures (āspin isomersā). The new cobalt(I) monocarbonyl complex LtBuCo(CO) (2) is a singlet (12) in the solid state, with an unprecedented diketiminate binding mode where one of the CāC double bonds of an aromatic ring completes a pseudo-square-planar coordination. Dissolving the compound gives a substantial population of the triplet (32), which has exceptionally large uniaxial zero-field splitting due to strong spināorbit coupling with a low-lying excited state. The interconversion of the two spin isomers is rapid, even at low temperature, and temperature-dependent NMR and electronic absorption spectroscopy studies show the energy differences quantitatively. Spectroscopically validated computations corroborate the presence of a low minimum-energy crossing point (MECP) between the two potential energy surfaces and elucidate the detailed pathway through which the Ī²-diketiminate ligand āslipsā between bidentate and arene-bound forms: rather than dissociation, the cobalt slides along the aromatic system in a pathway that balances strain energy and cobaltāligand bonding. These results show that multiple spin states are easily accessible in this hemilabile system and map the thermodynamics and mechanism of the transition
Planar three-coordinate iron sulfide in a synthetic [4Fe-3S] cluster with biomimetic reactivity
Ironāsulfur clusters are emerging as reactive sites for the reduction of small-molecule substrates. However, the four-coordinate iron sites of typical ironāsulfur clusters rarely react with substrates, implicating three-coordinate iron. This idea is untested because fully sulfide-coordinated three-coordinate iron is unprecedented. Here we report a new type of [4Fe-3S] cluster that features an iron centre with three bonds to sulfides, and characterize examples of the cluster in three oxidation levels using crystallography, spectroscopy, and ab initio calculations. Although a high-spin electronic configuration is characteristic of other ironāsulfur clusters, the three-coordinate iron centre in these clusters has a surprising low-spin electronic configuration due to the planar geometry and short Fe-S bonds. In a demonstration of biomimetic reactivity, the [4Fe-3S] cluster reduces hydrazine, a natural substrate of nitrogenase. The product is the first example of NH2 bound to an ironāsulfur cluster. Our results demonstrate that three-coordinate iron supported by sulfide donors is a plausible precursor to reactivity in ironāsulfur clusters like the FeMoco of nitrogenase