The reaction of carbon dioxide with hydrido-and dinitrogen complexes of iron

Bianco, V. D.; Doronzo, S.; Rossi, M.

doi:10.1016/s0022-328x(00)89809-5

Cited by 30 publications

(3 citation statements)

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“…One of the simplest CO 2 reduction reactions is its hydrogenation to formic acid . While a number of noble-metal catalysts for the hydrogenation of CO 2 to formic acid exist, − there are only a handful of examples using first-row transition metals such as iron − and cobalt, − and information about their thermodynamic properties and elementary reaction steps is needed. − For example, the hydricity (Δ G H – ), which is the heterolytic dissociation energy of [M–H] n + into M n + and H – (eq ), has only been experimentally determined for one iron hydride complex (FpH) despite recent reports of iron-catalyzed CO 2 hydrogenation. − Knowledge of the hydricities of hydrogenation catalysts can aid the design of new catalysts. This is highlighted by the recent work of Linehan and co-workers on a cobalt hydride catalyst, , in which the design of this efficient CO 2 -to-formate hydrogenation system was achieved, in part, by using a cobalt hydride that was more hydridic (i.e., <43 kcal/mol) than the formate (eq ). …”

Section: Introductionmentioning

confidence: 99%

“…35 Formal hydride transfer from phosphine-ligated iron hydride complexes to CO 2 to give formate is well-known. [29][30][31][32][33][34]55 A comparison of the hydricity of (SiP iPr 3 )Fe(H 2 )(H) to that of formate (eq 2) indicates that the reaction for hydride transfer from (SiP iPr 3 )Fe(H 2 )(H) to CO 2 to afford formate is endergonic by over 10 kcal/mol. Yet, as will be shown below, (SiP iPr 3 )Fe(H 2 )(H) can still react with CO 2 both stoichiometrically and catalytically to afford formate.…”

Section: ■ Introductionmentioning

confidence: 99%

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Hydricity of an Fe–H Species and Catalytic CO₂ Hydrogenation

2014

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Despite renewed interest in carbon dioxide (CO2) reduction chemistry, examples of homogeneous iron catalysts that hydrogenate CO2 are limited compared to their noble-metal counterparts. Knowledge of the thermodynamic properties of iron hydride complexes, including M–H hydricities (ΔG H– ), could aid in the development of new iron-based catalysts. Here we present the experimentally determined hydricity of an iron hydride complex: (SiP iPr 3)Fe(H2)(H), ΔG H– = 54.3 ± 0.9 kcal/mol [SiP iPr 3 = [Si(o-C6H4PiPr2)3]−]. We also explore the CO2 hydrogenation chemistry of a series of triphosphinoiron complexes, each with a distinct apical unit on the ligand chelate (Si–, C–, PhB–, N, B). The silyliron (SiPR 3)Fe (R = iPr and Ph) and boratoiron (PhBP iPr 3)Fe (PhBP iPr 3 = [PhB(CH2PiPr2)3]−) systems, as well as the recently reported (CP iPr 3)Fe (CP iPr 3 = [C(o-C6H4PiPr2)3]−), are also catalysts for CO2 hydrogenation in methanol and in the presence of triethylamine, generating methylformate and triethylammonium formate at up to 200 TON using (SiPPh 3)FeCl as the precatalyst. Under stoichiometric conditions, the iron hydride complexes of this series react with CO2 to give formate complexes. Finally, the proposed mechanism of the (SiP iPr 3)-Fe system proceeds through a monohydride intermediate (SiP iPr 3)Fe(H2)(H), in contrast to that of the known and highly active tetraphosphinoiron, (tetraphos)Fe (tetraphos = P(o-C6H4PPh2)3), CO2 hydrogenation catalyst.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Hydricity of an Fe–H Species and Catalytic CO₂ Hydrogenation

2014

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“…Carbon dioxide was also shown to react with solid, powdered H 2 Fe(N 2 )(PEtPh 2 ) 3 and H 2 Fe(H 2 )(PEtPh 2 ) 3 at room temperature with sunlight . No reaction occurred at 0 °C or in dark.…”

Section: Monodentate Ligand Systemsmentioning

confidence: 99%

Iron Dihydride Complexes: Synthesis, Reactivity, and Catalytic Applications

Dai

Guan

2017

Israel Journal of Chemistry

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Iron dihydride complexes often play important roles in catalytic reactions that employ reducing agents such as H 2 , boranes, and silanes. Development of more efficient and selective iron-based catalysts for these processes requires effective synthetic strategies and a deeper understanding of the reactivity of the dihydride complexes. The purpose of this review is to provide the readers with an overview of different ligand systems that have been used to support iron dihydride complexes. Figure 1. General reactivity of cis-and trans-FeH 2 beneficial to catalytic reduction.

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