What is the nature of bonding in [Fe(CO)3(NO)]− and [Fe(CO)4]2−?

Gruden, Maja; Zlatar, Matija

doi:10.1007/s00214-020-02639-3

Cited by 4 publications

(8 citation statements)

References 65 publications

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“…Here, we focus on the former because the Fe-CO bond in various complexes has already been the subject of a great number of computational studies. [23][24][25][26][27] By contrast, the metal-ligand bonding between Fe and thiochalcones has not been elucidated from a computational quantum chemical perspective so far. Thus, the interactions between the Fe center and the 1,3thiadiene ligands in 1-7 will be examined here using a wide variety of modern quantum chemical methods.…”

Section: Introductionmentioning

confidence: 99%

Metal–ligand bonding in tricarbonyliron(0) complexes bearing thiochalcone ligands

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Metal–ligand bonding in tricarbonyliron(0) complexes bearing thiochalcone ligands

et al. 2022

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“…93 Gruden and Zlatar performed a NOCV (natural orbitals for chemical valence) analysis on [Fe(CO) 3 ] 2− and NO + fragments, finding large charge flow from the Fe center to the NO + ligand, which was held as additional evidence that the iron center cannot be in an Fe(−II) formal oxidation state. 92 Furthermore, a comparison of this analysis with that of the analogue 1 seems to confirm the disparate electronic configurations of the iron centers in each species.…”

Section: Complexes Containing Carbonyl Ligandsmentioning

confidence: 63%

“…126,155 The hydride ligand gives rise to a strongly high-field shifted 1 H NMR resonance (δ = −13.1 ppm). 155 Compound 91 is the isocyano analogue of the carbonyl complex HCo(CO) 4 (92), known for its relevance in catalytic hydroformylation processes. 156,157 Hydride 91 reacts with H 2 (1 atm, r. t.…”

Section: 2]cryptand)][c 60mentioning

confidence: 99%

“…The spectroscopic evidence ( 57 Fe Mössbauer, EXAFS and XES spectroscopy) and the theoretical calculations (DFT, TDDFT, and CASSCF) are not only in agreement but consistent with the structural characterization (X-ray and FT-IR). , Based on their calculations, Plietker and co-workers suggested that in the ground-state the complex features an Fe(0) atom, and that the Fe–NO bond consists of two covalent π-bonds to an NO – moiety . Gruden and Zlatar performed a NOCV (natural orbitals for chemical valence) analysis on [Fe(CO) 3 ] 2– and NO + fragments, finding large charge flow from the Fe center to the NO + ligand, which was held as additional evidence that the iron center cannot be in an Fe(−II) formal oxidation state . Furthermore, a comparison of this analysis with that of the analogue 1 seems to confirm the disparate electronic configurations of the iron centers in each species.…”

Section: Synthesis and Basic Reactivity Patterns Of D-block Metalatesmentioning

confidence: 99%

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Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Landaeta,

Horsley Downie,

Wolf

2024

Chem. Rev.

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This review surveys the synthesis and reactivity of low-oxidation state metalate anions of the d-block elements, with an emphasis on contributions reported between 2006 and 2022. Although the field has a long and rich history, the chemistry of transition metalate anions has been greatly enhanced in the last 15 years by the application of advanced concepts in complex synthesis and ligand design. In recent years, the potential of highly reactive metalate complexes in the fields of small molecule activation and homogeneous catalysis has become increasingly evident. Consequently, exciting applications in small molecule activation have been developed, including in catalytic transformations. This article intends to guide the reader through the fascinating world of low-valent transition metalates. The first part of the review describes the synthesis and reactivity of d-block metalates stabilized by an assortment of ligand frameworks, including carbonyls, isocyanides, alkenes and polyarenes, phosphines and phosphorus heterocycles, amides, and redox-active nitrogen-based ligands. Thereby, the reader will be familiarized with the impact of different ligand types on the physical and chemical properties of metalates. In addition, ion-pairing interactions and metal−metal bonding may have a dramatic influence on metalate structures and reactivities. The complex ramifications of these effects are examined in a separate section. The second part of the review is devoted to the reactivity of the metalates toward small inorganic molecules such as H 2 , N 2 , CO, CO 2 , P 4 and related species. It is shown that the use of highly electron-rich and reactive metalates in small molecule activation translates into impressive catalytic properties in the hydrogenation of organic molecules and the reduction of N 2 , CO, and CO 2 . The results discussed in this review illustrate that the potential of transition metalate anions is increasingly being tapped for challenging catalytic processes with relevance to organic synthesis and energy conversion. Therefore, it is hoped that this review will serve as a useful resource to inspire further developments in this dynamic research field.

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“…However, despite the applications of hydroxamates, there is a dearth of literature on theoretical studies of hydroxamates, and this is due to the challenge in modeling transition metal complexes [15,19]. Nevertheless, DFT has been used in studying transition metal complexes [25,26]. Herein, we study four novel chemicals having to contain hydroxamic and carboxylic acid functional groups and analyze their chelating ability to Fe 2+, which is the state of iron in the pyrite scale.…”

Section: Introductionmentioning

confidence: 99%

Molecular Design of Novel Chemicals for Iron Sulfide Scale Removal

Onawole

Hussein

Nimir

et al. 2021

Journal of Chemistry

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Scale deposition is a pertinent challenge in the oil and gas industry. Scales formed from iron sulfide are one of the troublous scales, particularly pyrite. Moreover, the use of biodegradable environmentally friendly chemicals reduces the cost compared to the conventional removal process. In this work, the chelating abilities of four novel chemicals, designed using the in silico technique of density functional theory (DFT), are studied as potential iron sulfide scale removers. Only one of the chemicals containing a hydroxamate functional group had a good chelating ability with Fe2+. The chelating strength and ecotoxicological properties of this chemical were compared to diethylenetriaminepentaacetic acid (DTPA), an already established iron sulfide scale remover. The new promising chemical surpassed DTPA in being a safer chemical and having a greater binding affinity to Fe2+ upon optimization, hence, a better choice. The presence of oxime (-NHOH) and carbonyl (C=O) moieties in the new chemical showed that the bidentate form of chelation is favored. Moreover, the presence of an intramolecular hydrogen bond enhanced its chelating ability.

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What is the nature of bonding in [Fe(CO)3(NO)]− and [Fe(CO)4]2−?

Cited by 4 publications

References 65 publications

Metal–ligand bonding in tricarbonyliron(0) complexes bearing thiochalcone ligands

Metal–ligand bonding in tricarbonyliron(0) complexes bearing thiochalcone ligands

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis

Molecular Design of Novel Chemicals for Iron Sulfide Scale Removal

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