Iron Cyclopentadienone Complexes: Discovery, Properties, and Catalytic Reactivity

Quintard, Adrien; Rodríguez, Jean

doi:10.1002/anie.201310788

Cited by 173 publications

(91 citation statements)

References 108 publications

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“…More recently, many new catalytic applications of cyclopentadienone 1 and related complexes have been reported [32][33][34][35][36][37][38][39][40][41][42][43][44][45].…”

Section: Introductionmentioning

confidence: 99%

Microwave-assisted synthesis of cyclopentadienone iron tricarbonyl complexes: molecular structures of [{η4-C4R2C(O)C4H8}Fe(CO)3] (R = Ph, 2,4-F2C6H3, 4-MeOC6H4) and attempts to prepare Fe(II) hydroxycyclopentadienyl–hydride complexes

2018

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“…More recently, many new catalytic applications of cyclopentadienone 1 and related complexes have been reported [32][33][34][35][36][37][38][39][40][41][42][43][44][45].…”

Section: Introductionmentioning

confidence: 99%

Microwave-assisted synthesis of cyclopentadienone iron tricarbonyl complexes: molecular structures of [{η4-C4R2C(O)C4H8}Fe(CO)3] (R = Ph, 2,4-F2C6H3, 4-MeOC6H4) and attempts to prepare Fe(II) hydroxycyclopentadienyl–hydride complexes

2018

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“…3 Synthetic hydride complexes often contain strong-field organic or phosphine ligands and thus diamagnetic metal centers. 4 As on the other hand potential iron hydride intermediates within the catalytic cycle of the nitrogenase are expected to feature high-spin iron centers with coordination numbers less than five, Holland and coworkers have targeted the synthesis and investigation of low-coordinate, high-spin iron(II) hydride systems that became accessible utilizing the β -diketiminate ligand system ( I , see Figure 1). 5 …”

Section: Introductionmentioning

confidence: 99%

An iron(ii) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity

et al. 2016

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After lithiation of PYR-H2 (PYR = [(HCCMeNC6H3(iPr)2)2(C5H5-N)]2−) – the precursor of an expanded β-diketiminato ligand system with two binding pockets – with KN(TMS)2 the reaction of the resulting potassium salt with FeBr2 led to a dinuclear iron(II) bromide complex [(PYR)Fe(μ-Br)2Fe] (1). Through treatment with KHBEt3 the bromide ligands could be replaced by hydrides to yield [PYR)Fe2(μ-H)2] (2), a distorted analogue of known β-diketiminato iron hydride complexes, as evidenced by NMR, Mößbauer and X-ray absorption spectroscopy, as well as by its reactivity: For instance, 2 reacts with the proton source lutidinium triflate via protonation of the hydride ligands to form an iron(II) product [(PYR)Fe2(OTf)2] (4), while CO2 inserts into the Fe-H bonds generating the formate complex [(PYR)Fe2(μ-HCOO)2] (5); in the presence of traces of water partial hydrolysis occurs so that [(PYR)Fe2(μ-OH)(μ-HCOO)] (6) is isolated. Altogether, the iron(II) chemistry supported by the PYR2− ligand is distinctly different from the one of nickel(II), where both, the arrangement of the two binding pockets and the additional pyridyl donor led to diverging features as compared with the corresponding system based on the parent β-diketiminato ligand.

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“…[14,15] Berkessel has reported a related iron cyclopentadienone complex with a chiral phosphoramidite ligand, which was applied in the asymmetric reduction of ketones. [16] This type of iron cyclopentadienone catalysts can be seen as cheap and relatively easily accessible derivatives of the original ruthenium-based Shvo's catalyst (for a recent review see [17]). …”

Section: Introductionmentioning

confidence: 99%

Iron/Brønsted Acid Catalyzed Asymmetric Hydrogenation: Mechanism and Selectivity‐Determining Interactions

Hopmann

2015

Chemistry A European J

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Hydrogenation catalysts involving abundant base metals such as cobalt or iron are promising alternatives to precious metal systems. Despite rapid progress in this field, base metal catalysts do not yet achieve the activity and selectivity levels of their precious metal counterparts. Rational improvement of base metal complexes is facilitated by detailed knowledge about their mechanisms and selectivity-determining factors. The mechanism for asymmetric imine hydrogenation with Knölker's iron complex in presence of a chiral phosphoric acid is here investigated computationally at the DFT-D level of theory, with models of up to 160 atoms. The resting state of the system is found to be an adduct between the iron complex and the deprotonated acid. Rate-limiting H2 splitting is followed by a step-wise hydrogenation mechanism, where the phosphoric acid acts as the proton donor. C-H…O interactions between the phosphoric acid and the substrate are involved in the stereocontrol at the final hydride transfer step. Computed enantiomeric ratios show excellent agreement with experiment, indicating that DFT-D is able to correctly capture the selectivitydetermining interactions of this system.

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Iron Cyclopentadienone Complexes: Discovery, Properties, and Catalytic Reactivity

Cited by 173 publications

References 108 publications

Microwave-assisted synthesis of cyclopentadienone iron tricarbonyl complexes: molecular structures of [{η4-C4R2C(O)C4H8}Fe(CO)3] (R = Ph, 2,4-F2C6H3, 4-MeOC6H4) and attempts to prepare Fe(II) hydroxycyclopentadienyl–hydride complexes

Microwave-assisted synthesis of cyclopentadienone iron tricarbonyl complexes: molecular structures of [{η4-C4R2C(O)C4H8}Fe(CO)3] (R = Ph, 2,4-F2C6H3, 4-MeOC6H4) and attempts to prepare Fe(II) hydroxycyclopentadienyl–hydride complexes

An iron(ii) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity

Iron/Brønsted Acid Catalyzed Asymmetric Hydrogenation: Mechanism and Selectivity‐Determining Interactions

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