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Carbon dioxide binding at a Ni/Fe center: synthesis and characterization of Ni(?¹-CO₂-?C) and Ni-?-CO₂-?C:?²O,O'-Fe.

ABSTRACT: The degree of CO₂ activation can be tuned by incorporating a distinct electronic coordination environment at the nickel center. A mononuclear nickel carboxylate species (Ni-CO₂, 3) and a dinuclear nickel-iron carboxylate species (Ni-CO₂-Fe, 5) were prepared. The structure of 3 reveals a rare ?¹-?C binding mode of CO₂, while that of 5 shows bridging CO₂ binding (?₂-?C:?²O,O') between the nickel and iron, presented as the first example of a nickel-?-CO₂-iron species. The structural analyses of 3 and 5 based on XRD and DFT data reveal a higher degree of CO₂ activation in 5, imparted by the additional interaction with an iron ion.

SUBMITTER: Yoo C

PROVIDER: S-EPMC5458731 | biostudies-literature | 2017 Jan

REPOSITORIES: biostudies-literature

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Carbon dioxide binding at a Ni/Fe center: synthesis and characterization of Ni(η1-CO2-κC) and Ni-μ-CO2-κC:κ2O,O'-Fe.

Yoo Changho C Lee Yunho Y

Chemical science 20160830 1

The degree of CO2 activation can be tuned by incorporating a distinct electronic coordination environment at the nickel center. A mononuclear nickel carboxylate species (Ni-CO2, 3) and a dinuclear nickel-iron carboxylate species (Ni-CO2-Fe, 5) were prepared. The structure of 3 reveals a rare η1-κC binding mode of CO2, while that of 5 shows bridging CO2 binding (μ2-κC:κ2</su ...[more]

PMID: 28616135

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Project description:The mixed-valence triiron complexes [Fe3(CO)7-x (PPh3) x (μ-edt)2] (x = 0-2; edt = SCH2CH2S) and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2] (diphosphine = dppv, dppe, dppb, dppn) have been prepared and structurally characterized. All adopt an anti arrangement of the dithiolate bridges, and PPh3 substitution occurs at the apical positions of the outer iron atoms, while the diphosphine complexes exist only in the dibasal form in both the solid state and solution. The carbonyl on the central iron atom is semibridging, and this leads to a rotated structure between the bridged diiron center. IR studies reveal that all complexes are inert to protonation by HBF4·Et2O, but addition of acid to the pentacarbonyl complexes results in one-electron oxidation to yield the moderately stable cations [Fe3(CO)5(PPh3)2(μ-edt)2]+ and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2]+, species which also result upon oxidation by [Cp2Fe][PF6]. The electrochemistry of the formally Fe(I)-Fe(II)-Fe(I) complexes has been investigated. Each undergoes a quasi-reversible oxidation, the potential of which is sensitive to phosphine substitution, generally occurring between 0.15 and 0.50 V, although [Fe3(CO)5(PPh3)2(μ-edt)2] is oxidized at -0.05 V. Reduction of all complexes is irreversible and is again sensitive to phosphine substitution, varying between -1.47 V for [Fe3(CO)7(μ-edt)2] and around -1.7 V for phosphine-substituted complexes. In their one-electron-reduced states, all complexes are catalysts for the reduction of protons to hydrogen, the catalytic overpotential being increased upon successive phosphine substitution. In comparison to the diiron complex [Fe2(CO)6(μ-edt)], [Fe3(CO)7(μ-edt)2] catalyzes proton reduction at 0.36 V less negative potentials. Electronic structure calculations have been carried out in order to fully elucidate the nature of the oxidation and reduction processes. In all complexes, the HOMO comprises an iron-iron bonding orbital localized between the two iron atoms not ligated by the semibridging carbonyl, while the LUMO is highly delocalized in nature and is antibonding between both pairs of iron atoms but also contains an antibonding dithiolate interaction.

Project description:The asymmetric unit of the title compound, [{Sn(C4H9)2(C6H5COO)}2O]2, consists of two half molecules, completed by application of inversion symmetry. Both mol-ecules adopt a ladder structure typical for this class of dimeric tetra-organodistannoxane di-carboxyl-ates characterized by a centrosymmetric four-membered (Sn-O)2 ring of rhomboidal shape that is extended on both sides by folded six-membered Sn-O-C rings. To a first approximation, both kinds of Sn atoms (Sn i and Sn o ) are trigonal-bipyramidally coordinated. The bond angles between the n-butyl groups are widened [135.64 (7)-146.20 (7)°] in comparison with an ideal trigonal bipyramid. Sn-O bond lengths within the {R2SnO3} coordination sphere depend strongly on the position of the corresponding O atom - axial (ax) or equatorial (eq) - as well as on the functionality of the carboxyl-ate groups which exhibit μ2 (-COO i ) and μ1 (-COO o ) coordination modes, respectively. In summary, the following sequence of distances [mean values] is found: d(Sn o -Oμ3) eq [2.024 (2) Å] < d(Sn i -Oμ3) eq [2.044 (2) Å] < d(Sn i -Oμ3) ax [2.158 (6) Å] < d(Sn o -Oμ1-carb) ax [2.182 (6) Å] < d(Sn i -Oμ2-carb) ax [2.250 (2) Å] ≃ d(Sn o -Oμ2-carb) ax [2.247 (12) Å]. The n-butyl groups adopt an anti-anti conformation with exception of two disordered outer n-butyl groups of the second mol-ecule which exhibit gauche-anti and anti-gauche conformations. Weak intra-molecular Sn⋯O inter-actions between the different O atoms of the outer carboxyl groups with the inner, as well as outer, Sn atoms give rise to a strongly distorted octa-hedral coordination at these Sn atoms. Inter-molecular inter-actions between the individual mol-ecules are restricted to van der Waals and O⋯H-C inter-actions of which a nearly linear very short C-H⋯O contact between the H atom of the phenyl group of one of the mol-ecules with the outer non-coordinating C=O group of the other molecule is the most prominent. It gives rise to a chain-like arrangement of the mol-ecules along [111]. The two n-butyl groups attached to the outer Sn atom of one mol-ecule are disordered over two sets of sites with occupancies of 0.806 (3)/0.194 (3) and 0.702 (3)/0.298 (3).

Dataset Information

Carbon dioxide binding at a Ni/Fe center: synthesis and characterization of Ni(?¹-CO₂-?C) and Ni-?-CO₂-?C:?²O,O'-Fe.

Publications

Carbon dioxide binding at a Ni/Fe center: synthesis and characterization of Ni(η<sup>1</sup>-CO<sub>2</sub>-κ<i>C</i>) and Ni-μ-CO<sub>2</sub>-κ<i>C</i>:κ<sup>2</sup><i>O</i>,<i>O</i>'-Fe.

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Dataset Information

Carbon dioxide binding at a Ni/Fe center: synthesis and characterization of Ni(?1-CO2-?C) and Ni-?-CO2-?C:?2O,O'-Fe.

Publications

Carbon dioxide binding at a Ni/Fe center: synthesis and characterization of Ni(η<sup>1</sup>-CO<sub>2</sub>-κ<i>C</i>) and Ni-μ-CO<sub>2</sub>-κ<i>C</i>:κ<sup>2</sup><i>O</i>,<i>O</i>'-Fe.

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OmicsDI is part of the ELIXIR infrastructure

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Carbon dioxide binding at a Ni/Fe center: synthesis and characterization of Ni(?¹-CO₂-?C) and Ni-?-CO₂-?C:?²O,O'-Fe.