Snapshots of Complete Nitrogen Atom Transfer from an Iron(IV) Nitrido Complex

Scepaniak, Jeremiah J.; Bontchev, Ranko P.; Johnson, Dennis L.; Smith, Jeremy M.

doi:10.1002/ange.201102028

Cited by 40 publications

(9 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…6 Their reactivity was systematically surveyed for a number of transformations 3h. 6a, 7 The tetrahedral Fe IV nitride groups were found to at least partially decay by intermolecular reductive N–N coupling yielding Fe I ‐NN‐Fe I dimers, provided the steric demand of ligand does not prevent such bimolecular reactions 3e. 8…”

Section: Methodsmentioning

confidence: 99%

Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

2014

View full text Add to dashboard Cite

Cryogenically trapped Fe(V) nitride complexes with cyclam-based ligands were found to decay by bimolecular reactions, forming exclusively Fe(II) compounds. Characterization of educts and products by Mössbauer spectroscopy, mass spectrometry, and spectroscopy-oriented DFT calculations showed that the reaction mechanism is reductive nitride coupling and release of dinitrogen (2 Fe(V)≡N→Fe(II)-N=N-Fe(II)→2 Fe(II)+N2). The reaction pathways, representing an "inverse" of the Haber-Bosch reaction, were computationally explored in detail, also to judge the feasibility of yielding catalytically competent Fe(V)(N). Implications for the photolytic cleavage of Fe(III) azides used to generate high-valent Fe nitrides are discussed.

show abstract

Section: Methodsmentioning

confidence: 99%

Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

2014

View full text Add to dashboard Cite

show abstract

“…Smith and co-workers performed a detailed reactivity study on a range of iron(IV) nitride complexes, which were found to be reactive toward triphenylphosphine, 259,262 styrene, 263 CO, 264 and isonitriles 264 to form group-transfer products (Schemes 34 and 35). The reactions of 99 and 100 with phosphines gave the iron(II) complexes [PhB( R Im) 3 Fe-(NPPh 3 )].…”

Section: Complexes Of Ironmentioning

confidence: 99%

High-Oxidation-State 3d Metal (Ti–Cu) Complexes withN-Heterocyclic Carbene Ligation

et al. 2018

View full text Add to dashboard Cite

High-oxidation-state 3d metal species have found a wide range of applications in modern synthetic chemistry and materials science. They are also implicated as key reactive species in biological reactions. These applications have thus prompted explorations of their formation, structure, and properties. While the traditional wisdom regarding these species was gained mainly from complexes supported by nitrogen- and oxygen-donor ligands, recent studies with N-heterocyclic carbenes (NHCs), which are widely used for the preparation of low-oxidation-state transition metal complexes in organometallic chemistry, have led to the preparation of a large variety of isolable high-oxidation-state 3d metal complexes with NHC ligation. Since the first report in this area in the 1990s, isolable complexes of this type have been reported for titanium(IV), vanadium(IV,V), chromium(IV,V), manganese(IV,V), iron(III,IV,V), cobalt(III,IV,V), nickel(IV), and copper(II). With the aim of providing an overview of this intriguing field, this Review summarizes our current understanding of the synthetic methods, structure and spectroscopic features, reactivity, and catalytic applications of high-oxidation-state 3d metal NHC complexes of titanium to copper. In addition to this progress, factors affecting the stability and reactivity of high-oxidation-state 3d metal NHC species are also presented, as well as perspectives on future efforts.

show abstract

“…C–N bond formation was also observed upon treatment of this Fe-nitride species with CO and with tert -butyl isocyanide (Figure 2a). 22 These latter reactions indicate that the iron(IV) nitride can be electrophilic. Similarly, an iron(V)-nitride species reacts with water and cobaltocene to give ammonia, suggesting the formation of a Brønsted base in situ .…”

Section: Dinitrogen Reduction and Functionalization At Fementioning

confidence: 99%

Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron

2013

View full text Add to dashboard Cite

The reduction of gaseous nitrogen (N2) is a challenge for industrial, biological and synthetic chemists, who want to understand the formation of ammonia (NH3) for agriculture and also want to form N-C and N-Si bonds for fine chemical synthesis. The iron-molybdenum active site of nitrogenase has inspired chemists to explore the ability of iron and molybdenum complexes to bring about transformations related to N2 reduction. This area of research has gained significant momentum, and the last two years have witnessed a number of significant advances in synthetic Fe-N2 and Mo-N2 chemistry. In addition, the identities of all atoms in the iron-molybdenum cofactor of nitrogenase have finally been elucidated, and the discovery of a carbide has generated new questions and targets for coordination chemists. This Perspective summarizes the recent work on iron and molydenum complexes, and highlights the opportunities for continued research.

show abstract

Snapshots of Complete Nitrogen Atom Transfer from an Iron(IV) Nitrido Complex

Cited by 40 publications

References 28 publications

Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis

High-Oxidation-State 3d Metal (Ti–Cu) Complexes withN-Heterocyclic Carbene Ligation

Recent developments in the homogeneous reduction of dinitrogen by molybdenum and iron

Contact Info

Product

Resources

About