Fluoro Nitrenoid Complexes FN=MF2 (M=Co,Rh, Ir): Electronic Structure Dichotomy and Formation of Nitrido Fluorides N≡MF3

The fluoronitrenoid metal complexes FNCoF₂ and FNRhF₂ as well as the first ternary Rh^VI and Ir^VI complexes NIrF₃ and NRhF₃ are described. They were obtained by the reaction of excited Group-9 metal atoms with NF₃ and their IR spectra, isolated in solid rare gases (neon and argon), were recorded. Aided by the observed ^14/15N isotope shifts and quantum-chemical predictions, all four stretching fundamentals of the novel complexes were safely assigned. The F−N stretching frequencies of the fluoronitrenoid complexes FNCoF₂ (1056.8 cm⁻¹) and FNRhF₂ (872.6 cm⁻¹) are very different and their N−M bonds vary greatly. In FNCoF₂, the FN ligand is singly bonded to Co and bears considerable iminyl/nitrene radical character, while the N−Rh bond in FNRhF₂ is a strong double bond with comparatively strong σ- and π-bonds. The anticipated rearrangement of FNCoF₂ to the nitrido Co^VI complex is predicted to be endothermic and was not observed.     

Dispersion Forces,Disproportionation, and Stable High‐Valent Late Transition Metal Alkyls

The transition metal tetra‐ and trinorbornyl bromide complexes, M(nor)₄ (M=Fe, Co, Ni) and Ni(nor)₃Br (nor=1‐bicyclo[2.2.1]hept‐1‐yl) and their homolytic fragmentations were studied computationally using hybrid density functional theory (DFT) at the B3PW91 and B3PW91‐D3 dispersion‐corrected levels. Experimental structures were well replicated; the dispersion correction resulted in shortened M?C bond lengths for the stable complexes, and it was found that Fe(nor)₄ receives a remarkable 45.9 kcal mol^?1 stabilization from the dispersion effects whereas the tetragonalized Co(nor)₄ shows stabilization of 38.3 kcal mol^?1. Ni(nor)₄ was calculated to be highly tetragonalized with long Ni?C bonds, providing a rationale for its current synthetic inaccessibility. Isodesmic exchange evaluation for Fe(nor)₄ confirmed that dispersion force attraction between norbornyl substituents is fundamental to the stability of these species.     

Non-Dissociative Activation of Chemisorbed Dinitrogen on One or Two Vanadium Atoms Supported by a Mo6S8 Cluster

Adsorption of N₂ on Mo₆S₈^q_V_x clusters (x=0, 1, 2; q=0, ±1) were systematically studied by density functional theory calculations with dispersion corrections. It was found that the N₂ can be chemisorbed and undergo non-dissociative activation on single or double metal atoms. The adsorption and activation are influenced by metal types (V or Mo), N₂ coordination modes and charge states of the clusters. Particularly, anionic Mo₆S₈⁻_V₂ clusters have remarkable ability to fix and activate N₂. In Mo₆S₈⁻_V₂, two V atoms prefer to adsorb on two adjacent S−Mo−S hollow sites, leading to the formation of a supported V…V unit. The N₂ is bridged side-on coordinated with these two V atoms with high adsorption energy and significant charge transfer. The bond order, bond length and vibration frequency of the adsorbed N₂ are close to those of a N−N single bond.     

High-Spin Iron(VI), Low-Spin Ruthenium(VI), and Magnetically Bistable Osmium(VI) in Molecular Group 8 Nitrido Trifluorides NMF3

Pseudo-tetrahedral nitrido trifluorides N≡MF₃ (M=Fe, Ru, Os) and square pyramidal nitrido tetrafluorides N≡MF₄ (M=Ru, Os) were formed by free-metal-atom reactions with NF₃ and subsequently isolated in solid neon at 5 K. Their IR spectra were recorded and analyzed aided by quantum-chemical calculations. For a d² electron configuration of the N≡MF₃ compounds in C_3v symmetry, Hund's rule predict a high-spin ³A₂ ground state with two parallel spin electrons and two degenerate metal d(δ)-orbitals. The corresponding high-spin ³A₂ ground state was, however, only found for N≡FeF₃, the first experimentally verified neutral nitrido Fe^VI species. The valence-isoelectronic N≡RuF₃ and N≡OsF₃ adopt different angular distorted singlet structures. For N≡RuF₃, the triplet ³A₂ state is only 5 kJ mol⁻¹ higher in energy than the singlet ¹A′ ground state, and the magnetically bistable molecular N≡OsF₃ with two distorted near degenerate ¹A′ and ³A“ electronic states were experimentally detected at 5 K in solid neon.     

On the Extreme Oxidation States of Iridium

It has recently been suggested that the oxidation states of Ir run from the putative ?III in the synthesized solid Na₃[Ir(CO)₃] to the well‐documented +IX in the species IrO₄⁺. Furthermore, [Ir(CO)₃]^3? was identified as an 18‐electron species. A closer DFT study now finds support for this picture: The orbitals spanned by the 6s,6p,5d orbitals of the iridium are all occupied. Although some have considerable ligand character, the deviations from 18 e leave the orbital symmetries unchanged. The isoelectronic systems from Os^?IV to Au^?I behave similarly, suggesting further possible species. To paraphrase Richard P. Feynmann “there is plenty of room at the bottom”.     

Cobalt‐Catalyzed Transformation of Molecular Dinitrogen into Silylamine under Ambient Reaction Conditions

The first successful example of cobalt‐catalyzed reduction of N₂ with Me₃SiCl and Na as a reductant, under ambient reaction conditions, gives N(SiMe₃)₃, which can be readily converted into NH₃. In this reaction system, 2,2′‐bipyridine (bpy) is found to work as an effective additive to improve substantially the catalytic activity. Co?N₂ complexes bearing three Me₃Si groups as ancillary ligands are considered to work as key reactive species based on DFT calculations. The DFT results also allow the proposal of a detailed reaction pathway for the transformation of N₂ into N(SiMe₃)₃.     

Probing the Potential of Hitherto Unexplored Base-Stabilized Borylenes in Dinitrogen Binding

Computational investigations were carried out to probe the potential of several dicoordinate, singly base-stabilized borylenes of the form [L→BR] (L=neutral Lewis base) in dinitrogen binding. The calculated reaction free energies and activation barriers associated with the formation of mono- and diborylene-N₂ adducts suggest the presence of thermally surmountable kinetic barriers towards their possible isolation. Our results show that the exergonicity of dinitrogen activation and fixation is linearly dependent on the natural charge at the boron center, which can be tuned to design novel boron-based compounds with potential applications to small-molecule activation. EDA-NOCV analysis reveals strong binding of dinitrogen to these base-stabilized borylenes.     

Tracing the Route to Ammonia: A Theoretical Study on the Possible Pathways for Dinitrogen Reduction with Tripodal Iron Complexes

The chemistry of nitrogen fixation has been the subject of considerable research with a view to gaining a proper understanding of the mechanistic details. In this article, density functional calculations are performed on all the mechanistic possibilities for dinitrogen reduction mediated by the tripodal iron complexes [(SiP^Me₃)Fe^I] ( [Fe_Si] ) and [(BP^Me₃)Fe⁰] ( [Fe_B] ). Dinitrogen addition to the neutral bare complex is found to be thermodynamically more favorable than that to the anionic one. Both symmetric and asymmetric pathways, along with the possible intermediates and transition states, are considered in this study. For both systems, the symmetric path is found to be more likely, although the prospect of the asymmetric path cannot be ignored. Moreover, interconversions between these two pathways are found to be less likely. This study corroborates most experimental observations and provides theoretical insight into the possible existence of some hitherto unknown intermediates such as multiple‐bonded Fe? N species in a trigonal bipyramidal geometry. Furthermore, in agreement with experimental observations, this study also highlights the possibility of hydrogen and hydrazine evolution during the complete reduction of dinitrogen.     

Polyfluorides and Neat Fluorine as Host Material in Matrix‐Isolation Experiments

The use of neat fluorine in matrix isolation is reported, as well as the formation of polyfluoride monoanions under cryogenic conditions. Purification procedures and spectroscopic data of fluorine are described, and matrix shifts of selected molecules and impurities in solid fluorine are compared to those of common matrix gases (Ar, Kr, N₂, Ne). The reaction of neat fluorine and IR‐laser ablated metal atoms to yield fluorides of chromium (CrF₅), palladium (PdF₂), gold (AuF₅), and praseodymium (PrF₄) has been investigated. The fluorides have been characterized in solid fluorine by IR spectroscopy at 5 K. Also the fluorination of Kr and the photo‐dismutation of XeO₄ have been studied by using IR spectroscopy in neat fluorine. Formation of the [F₅]^? ion was obtained by IR‐laser ablation of platinum in the presence of fluorine and proven in a Ne matrix at 5 K by two characteristic vibrational bands of [F₅]^? at $\tilde \nu $ =850.7 and 1805.0 cm^?1 and its photo‐behavior.     

Single-Atom Catalysis Using Chromium Embedded in Divacant Graphene for Conversion of Dinitrogen to Ammonia

Reduction of dinitrogen to ammonia under ambient conditions is a long-standing challenge. The few metal-based catalysts proposed have conspicuous disadvantages such as high cost, high energy consumption, and being hazardous to the environment. Single-atom catalysis has emerged as a new frontier in heterogeneous catalysis and metal atoms atomically dispersed on supports receive more and more attention owing to rapid advances in synthetic methodologies and computational modeling. Herein, we propose metal atoms embedded in divacant graphene as a catalyst for N₂ fixation based on density functional calculations. We systematically investigate the potential of using transition metal like Cr, Mn, Fe, Mo and Ru as catalysts and our study reveals that Cr embedded in graphene exhibit good catalytic activity for N₂ fixation. The synergy between the metal atoms and graphene surface provides a stable support to the metal center that has a high spin density to promote adsorption of N₂ and activation of its N≡N triple bond. Our study deciphers the mechanism of conversion of N₂ to ammonia following two possible reaction pathways, distal and enzymatic routes, via sequential protonation and reduction of activated N₂. The study provides a rational framework for conversion of dinitrogen to ammonia using single atom catalyst.     

Nitrogen fixation under mild ambient conditions: part I--the initial dissociation/association step at molybdenum triamidoamine complexes

In several recent studies Schrock and collaborators demonstrated for the first time how molecular dinitrogen can be catalytically transformed under mild and ambient conditions to ammonia by a molybdenum triamidoamine complex. In this work, we investigate the geometrical and electronic structures involved in this process of dinitrogen activation with quantum chemical methods. Density functional theory (DFT) has been employed to calculate the coordination energies of ammonia and dinitrogen relevant for the dissociation/association step in which ammonia is substituted by dinitrogen. In the DFT calculations the triamidoamine chelate ligand has been modeled by a systematic hierarchy of increasingly complex substituents at the amide nitrogen atoms. The most complex ligand considered is an experimentally known ligand with an HMT = 3,5-(2,4,6-Me3C6H2)2C6H3 substituent. Several assumptions by Schrock and collaborators on key reaction steps are confirmed by our calculations. Additional information is provided on many species not yet observed experimentally. Particular attention is paid to the role of the charge of the complexes. The investigation demonstrates that dinitrogen coordination is enhanced for the negatively charged metal fragment, that is, coordination is more favorable for the anionic metal fragment than for the neutral species. Coordination of N2 is least favorable for the cationic metal fragment. Furthermore, ammonia abstraction from the cationic complex is energetically unfavorable, while NH3 abstraction is less difficult from the neutral and easily feasible from the anionic low-spin complex.     

Directionality of Dihydrogen Bonds: The Role of Transition Metal Atoms

A theoretical study on two series of electron‐rich group 8 hydrides is carried out to evaluate involvement of the transition metal in dihydrogen bonding. To this end, the structural and electronic parameters are computed at the DFT/B3PW91 level for hydrogen‐bonded adducts of [(PP₃)MH₂] and [Cp*MH(dppe)] (M=Fe, Ru, Os; PP₃=κ⁴‐P(CH₂CH₂PPh₂)₃, dppe= κ²‐Ph₂PCH₂CH₂PPh₂) with CF₃CH₂OH (TFE) as proton donor. The results are compared with those of adduct [Cp₂NbH₃] ? TFE featuring a “pure” dihydrogen bond, and classical hydrogen bonds in pyridine ? TFE and Me₃N ? TFE. Deviation of the H ??? H? A fragment from linearity is shown to originate from the metal participation in dihydrogen bonding. The latter is confirmed by the electronic parameters obtained by NBO and AIM analysis. Considered together, orbital interaction energies and hydrogen bond ellipticity are salient indicators of this effect and allow the MH ??? HA interaction to be described as a bifurcate hydrogen bond. The impact of the M ??? HA interaction is shown to increase on descending the group, and this explains the experimental trends in mechanisms of proton‐transfer reactions via MH ??? HA intermediates. Strengthening of the M ??? H interaction in the case of electron‐rich 5d metal hydrides leads to direct proton transfer to the metal atom.     

Elucidating the Coordination Chemistry and Mechanism of Biological Nitrogen Fixation

How does the enzyme nitrogenase reduce the inert molecule N₂ to NH₃ under ambient conditions that are so different from the energy‐expensive conditions of the best industrial practices? This review focuses on recent theoretical investigations of the catalytic site, the iron–molybdenum cofactor FeMo‐co, and the way in which it is hydrogenated by protons and electrons and then binds N₂. Density functional calculations provide reaction profiles and activation energies for possible mechanistic steps. This establishes a conceptual framework and the principles for the coordination chemistry of FeMo‐co that are essential to the chemical mechanism of catalysis. The model advanced herein explains relevant experimental data.     

Fluorine... and pi...alkali metal interactions control in the stereoselective amide enolate alkylation with fluorinated oxazolidines (Fox) as a chiral auxiliary: an experimental and theoretical study

The alpha-alkylation of amide enolates by using a pseudo-C(2) symmetry trans 4-phenyl-2-trifluoromethyloxazolidine (trans-Fox) as a chiral auxiliary occurs with an extremely high diastereoselectivity (>99 % de). The origin of this excellent stereocontrol was investigated by an experimental and theoretical (DFT) study. With this trans chiral auxiliary, both F...metal and pi...metal interactions compete to give the same diastereomer through Re face alkylation of the enolate. A 5.5 kcal mol(-1) energy difference found between the Re face and the Si face attack transition states is consistent with the complete diastereoselectivity that has been experimentally achieved. On the other hand, in the case of the cis chiral auxiliary (cis-Fox) the competition between the F...metal and pi...metal interactions is unfavourable to the diastereoselectivity. In this case, the Re face and the Si face attack transition states were found to be nearly isoenergetic (0.3 kcal mol(-1) difference), which is in good agreement with the very low diastereoselectivity observed.