Double donation in trigonal planar iron–carbodiphosphorane complexes – a concise study on their spectroscopic and electronic properties

Kneusels, Nis-Julian H.; Münzer, Jörn E.; Flosdorf, Kimon; Jiang, Daifeng; Neumüller, Bernhard; Zhao, Lili; Eichhöfer, Andreas; Frenking, Gernot; Kuzu, Istemi

doi:10.1039/c9dt04725e

Cited by 21 publications

(16 citation statements)

References 106 publications

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“…32 However, carbodiphosphorane ligands have been used for the synthesis and characterization of low-coordinate Fe(II) complexes. 33,34 Given the rich redox chemistry of the reported sixcoordinate complexes of chromium, iron, and cobalt with the bis(pyridine)carbodicarbene ligand (Figure 1), 6,7 we probed the redox properties of the nickel compound 3-BF 4 using cyclic voltammetry (Figure 3). We observed a reversible redox couple at 0.4 V and an irreversible wave at −2 V. We assign the reversible redox couple at 0.4 V to a one-electron oxidation of compound 3-BF 4 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis and Characterization of Bis(phosphine)carbodicarbene Complexes of Iron, Cobalt, and Nickel

Zhang

Krogman

2021

Organometallics

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The synthesis and characterization of nickel, cobalt, and iron complexes of the bis(phosphine)carbodicarbene (CDC) ligand 1 is described. The square-planar complexes can be synthesized without the isolation of the deprotonated carbodicarbene ligand, and three different synthetic methods were used to make these first-row transition-metal compounds. The reaction between ligand 1-BPh 4 and Ni(COD) 2 afforded the compound [(CDC)Ni(η 1 -C 8 H 13 )][BPh 4 ] (2-BPh 4 ) via the insertion of COD into the Ni−H bond produced by cyclometalation. The complexes [(CDC)MCl] + for nickel and cobalt were synthesized from the reaction of carbodicarbene ligand 1 with NiCl 2 or CoCl 2 in the presence of triethylamine. For the synthesis of the iron coordination complex of CDC ligand 1, Fe 2 Mes 4 was used to produce [(CDC)Fe-Mes][BPh 4 ] (5), an intermediate-spin Fe(II) compound. Complexes 3−7 were characterized by spectroscopic methods and X-ray single-crystal diffraction analysis.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis and Characterization of Bis(phosphine)carbodicarbene Complexes of Iron, Cobalt, and Nickel

Zhang

Krogman

2021

Organometallics

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“…Readers are further referred to the recent review articles to learn more about the EDA‐NOCV method and its application [45–46] . The EDA‐NOCV method was recently used to investigate the Fe−C carbone interaction in a high spin Fe(II)‐complex [46] …”

Section: Methodsmentioning

confidence: 99%

“…[45][46] The EDA-NOCV method was recently used to investigate the FeÀ C carbone interaction in a high spin Fe(II)-complex. [46]…”

Section: Methodsmentioning

confidence: 99%

Dinitrogen Binding Relevant to FeMoco of Nitrogenase: Clear Visualization of σ‐Donation and π‐Backdonation from Deformation Electron Densities around Carbon/Silicon‐Iron Site

2022

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Dinitrogen (N2) binding and electron transfer reduction of N2 to ammonia (NH3) by the FeMoco cofactor of the nitrogenase enzyme are captivating. They are a part of the textbook for general chemistry. The nature of N2 bonding by reduced FeMoco is speculated based on the experimental evidence. The inorganic core MoFe7S9C1− possesses a Fe6(μ6‐C4−) unit. The mode of N2‐binding at one of the Fe‐centers of the elusive Fe6(μ6‐C4−) unit and the role of light element C4− is intriguing. In the past, the mode of N2‐binding and the kinetics of N2 reduction have been studied by spectroscopic and other tools. Herein, we report on the energy decomposition analysis coupled with natural orbital for chemical valence (EDA‐NOCV) calculations/analyses to shed light on the deeper insight of the N2 binding and especially on the influence of the C‐atom of previously reported Fe‐complexes with an EP3 donor set (E=C, Si). The role of the C‐atom in the iron‐carbon site has been studied by elaboration with deformation electron densities. The intrinsic interaction energy of the bond between Fe and N2 and pairwise orbital interactions between them have been quantitatively estimated. The influence of σ‐donation of three phosphine ligands and their effects on the Fe−N2 bond have been thoroughly studied.

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“…The EDA-NOCV method 28 − 37 is more appropriate in explaining the nature of the bond as one of the major strengths of the method is its ability to provide the best bonding model to represent the bonding situation in the equilibrium geometry. 35 , 36 However, the EDA-NOCV analysis of paramagnetic species is quite challenging as the main problem of EDA-NOCV calculations of paramagnetic species is to reflect physically meaningful orbital occupations in both possible situations: the bound complex and the isolated fragments.…”

Section: Computational Methodsmentioning

confidence: 99%

“… 36 The N 2 has been considered in singlet, and ligand-Fe is either in S = 1 or in 1/2 or 3/2 spin state for our EDA-NOCV fragmentations and analyses. 37 …”

Section: Computational Methodsmentioning

confidence: 99%

Estimations of Fe–N₂ Intrinsic Interaction Energies of Iron–Sulfur/Nitrogen–Carbon Sites: A Deeper Bonding Insight by EDA-NOCV Analysis of a Model Complex of the Nitrogenase Cofactor

Gorantla

Mondal

2021

ACS Omega

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The MoFe 7 S 9 C 1– unit of the nitrogenase cofactor (FeMoco) attracts chemists and biochemists due to its unusual ability to bind aerial dinitrogen (N 2 ) at ambient condition and catalytically convert it into ammonia (NH 3 ). The mode of N 2 binding and its reaction pathways are yet not clear. An important conclusion has been made based on the very recent synthesis and isolation of model Fe(I/0)-complexes with sulfur-donor ligands under the cleavage of one Fe–S bond followed by binding of N 2 at the Fe(0) center. These complexes are structurally relevant to the nitrogenase cofactor (MoFe 7 S 9 C 1– ). Herein, we report the EDA-NOCV analyses and NICS calculations of the dinitrogen-bonded dianionic complex Fe 0 –N 2 ( 1 ) (having a C Ar ← Fe π-bond) and monoanionic complex Fe I –N 2 ( 2 ) (having a C Ar –Fe σ-bond) to provide a deeper insight into the Fe–N 2 interacting orbitals and corresponding pairwise interaction energies (EDA-NOCV = energy decomposition analysis coupled with natural orbital for chemical valence; NICS = nucleus-independent chemical shifts). The orbital interaction in the Fe–N 2 bond is significantly larger than Coulombic interactions, with major pairwise contributions coming from d(Fe) orbitals to the empty π* orbitals of N 2 (three Fe → N 2 ). Δ E int values are in the range of −61 to −77 kcal mol –1 . Very interestingly, NICS calculations have been carried out for the fragments before and after binding of the N 2 molecule. The computed σ- and π-aromaticity values are attributed to the position of the Fe atoms, oxidation states of Fe centers, and Fe–C bond lengths of these two complexes.

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Double donation in trigonal planar iron–carbodiphosphorane complexes – a concise study on their spectroscopic and electronic properties

Abstract: Trigonal planar carbodiphosphorane (CDP) iron(ii) complexes [CDPR-Fe{N(SiMe3)2}2] (CDPR: R = Ph or Me) with high spin configurations are presented.

Cited by 21 publications

References 106 publications

Synthesis and Characterization of Bis(phosphine)carbodicarbene Complexes of Iron, Cobalt, and Nickel

Synthesis and Characterization of Bis(phosphine)carbodicarbene Complexes of Iron, Cobalt, and Nickel

Dinitrogen Binding Relevant to FeMoco of Nitrogenase: Clear Visualization of σ‐Donation and π‐Backdonation from Deformation Electron Densities around Carbon/Silicon‐Iron Site

Estimations of Fe–N₂ Intrinsic Interaction Energies of Iron–Sulfur/Nitrogen–Carbon Sites: A Deeper Bonding Insight by EDA-NOCV Analysis of a Model Complex of the Nitrogenase Cofactor

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Double donation in trigonal planar iron–carbodiphosphorane complexes – a concise study on their spectroscopic and electronic properties

Abstract: Trigonal planar carbodiphosphorane (CDP) iron(ii) complexes [CDPR-Fe{N(SiMe3)2}2] (CDPR: R = Ph or Me) with high spin configurations are presented.

Cited by 21 publications

References 106 publications

Synthesis and Characterization of Bis(phosphine)carbodicarbene Complexes of Iron, Cobalt, and Nickel

Synthesis and Characterization of Bis(phosphine)carbodicarbene Complexes of Iron, Cobalt, and Nickel

Dinitrogen Binding Relevant to FeMoco of Nitrogenase: Clear Visualization of σ‐Donation and π‐Backdonation from Deformation Electron Densities around Carbon/Silicon‐Iron Site

Estimations of Fe–N2 Intrinsic Interaction Energies of Iron–Sulfur/Nitrogen–Carbon Sites: A Deeper Bonding Insight by EDA-NOCV Analysis of a Model Complex of the Nitrogenase Cofactor

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Estimations of Fe–N₂ Intrinsic Interaction Energies of Iron–Sulfur/Nitrogen–Carbon Sites: A Deeper Bonding Insight by EDA-NOCV Analysis of a Model Complex of the Nitrogenase Cofactor