Iron Imido Complexes Research Articles

Square-planar iron imido complexes containing strong-field pincer ligands as models for active species in catalytic nitrene transfer

Treatment of the iron(I) precursor, [Fe(N2)(tBuPNP)] (tBuPNP = anion of 2,5-bis(di-tert-butylphosphinomethyl)pyrrole), with mesitylazide (mesityl = 2,4,6-trimethylphenyl) results in the formation of a new four-coordinate iron imido complex, [Fe(NMes)(tBuPNP)], which serves as a model for reactive metal-nitrene intermediates in catalytic C–H amination. The solid-state structure of the complex exhibits a rare square-planar geometry about the iron center with a nearly linear imido unit. In analogy to similar compounds of cobalt, the electronic structure of [Fe(NMes)(tBuPNP)] is assigned as low-spin Fe(II) ferromagnetically coupled to a nitrene radical giving an overall S = 3/2 groundstate. A similar imido species was detected spectroscopically by treatment of [Fe(N2)(tBuPNP)] with 1-adamantylazide, however, use of the less bulky nitrene source phenylazide results in formation of the tetrazido species, [Fe(κ2-N4Ph2)(tBuPNP)]. Unexpectedly, [Fe(NMes)(tBuPNP)] proved recalcitrant toward nitrene transfer reactions involving weak C–H bonds, but did react readily with CO to generate [Fe(CO)2(tBuPNP)]. The reactivity of the new imido species in the context of its unique geometry and electronic structure is discussed.

From Divalent to Pentavalent Iron Imido Complexes and an Fe(V) Nitride via N-C Bond Cleavage.

As key intermediates in metal-catalyzed nitrogen-transfer chemistry, terminal imido complexes of iron have attracted significant attention for a long time. In search of versatile model compounds, the recently developed second-generation N-anchored tris-NHC chelating ligand tris-[2-(3-mesityl-imidazole-2-ylidene)-methyl]amine (TIMMNMes) was utilized to synthesize and compare two series of mid- to high-valent iron alkyl imido complexes, including a reactive Fe(V) adamantyl imido intermediate en route to an isolable Fe(V) nitrido complex. The chemistry toward the iron adamantyl imides was achieved by reacting the Fe(I) precursor [(TIMMNMes)FeI(N2)]+ (1) with 1-adamantyl azide to yield the corresponding trivalent iron imide. Stepwise chemical reduction and oxidation lead to the isostructural series of low-spin [(TIMMNMes)Fe(NAd)]0,1+,2+,3+ (2Ad-5Ad) in oxidation states II to V. The Fe(V) imide [(TIMMNMes)Fe(NAd)]3+ (5Ad) is unstable under ambient conditions and converts to the air-stable nitride [(TIMMNMes)FeV(N)]2+ (6) via N-C bond cleavage. The stability of the pentavalent imide can be increased by derivatizing the nitride [(TIMMNMes)FeIV(N)]+ (7) with an ethyl group using the triethyloxonium salt Et3OPF6. This gives access to the analogous series of ethyl imides [(TIMMNMes)Fe(NEt)]0,1+,2+,3+ (2Et-5Et), including the stable Fe(V) ethyl imide. Iron imido complexes exist in a manifold of different electronic structures, ultimately controlling their diverse reactivities. Accordingly, these complexes were characterized by single-crystal X-ray diffraction analyses, SQUID magnetization, and electrochemical methods, as well as 57Fe Mössbauer, IR vibrational, UV/vis electronic absorption, multinuclear NMR, X-band EPR, and X-ray absorption spectroscopy. Our studies are complemented with quantum chemical calculations, thus providing further insight into the electronic structures of all complexes.

Nonheme Iron Imido Complexes Bearing a Non-Innocent Ligand: A Synthetic Chameleon Species in Oxidation Reactions.

High-valent iron-imido complexes can perform C-H activation and sulfimidation reactions, but are far less studied than the more ubiquitous iron-oxo species. As case studies, we have looked at a recently published iron(V)-imido ligand π-cation radical complex, which is formally an iron(VI)-imido complex [FeV (NTs)(TAML+. )] (1; NTs=tosylimido), and an iron(V)-imido complex [FeV (NTs)(TAML)]- (2). Using a theoretical approach, we found that they have multiple energetically close-lying electromers, sometimes even without changing spin states, reminiscent of the so-called Compound I in Cytochrome P450. When studying their reactivity theoretically, it is indeed found that their electronic structures may change to perform efficient oxidations, emulating the multi-spin state reactivity in FeIV O systems. This is actually in contrast to the known [FeV (O)(TAML)]- species (3), where the reactions occur only on the ground spin state. We also looked into the whole reaction pathway for the C-H bond activation of 1,4-cyclohexadiene by these intermediates to reproduce the experimentally observed products, including steps that usually attract no interest (neither theoretically nor experimentally) due to their non-rate-limiting status and fast reactivity. A new "clustering non-rebound mechanism" is presented for this C-H activation reaction.

Toward understanding highly electron-withdrawing terminal Fe(IV) imides

Terminal iron imido complexes with highly electron-withdrawing <i>N</i>-substituents have remained elusive despite their proposed implication in <i>N</i>-group-transfer chemistry. In a recent issue of <i>Cell Reports Physical Science</i>, Deng and co-workers report the isolation and characterization of an <i>N</i>-trifluoromethyl-substituted Fe(IV) bis-imido species that displays a triplet ground state and undergoes intramolecular C‒H activation.

A Two-Coordinate Iron(II) Imido Complex with NHC Ligation: Synthesis, Characterization, and Its Diversified Reactivity of Nitrene Transfer and C-H Bond Activation.

Iron terminal imido species are typically implicated as reaction intermediates in iron-catalyzed transformations. While a large body of work has been devoted to mid- and high-valent iron imidos, to date the chemistry of iron(II) imidos has remained largely unexplored due to the difficulty in accessing them. Herein, we present a study on the two-coordinate iron(II) imido complex [(IPr)Fe(NArTrip)] (3; IPr = 1,3-bis(2′,6′-diisopropylphenyl)imidazol-2-ylidene; ArTrip = 2,6-bis(2′,4′,6′-triisopropylphenyl)phenyl) prepared from the reaction of an iron(0) complex with the bulky azide ArTripN3. Spectroscopic investigations in combination with DFT calculations established a high-spin S = 2 ground spin state for 3, consistent with its long Fe–N multiple bond of 1.715(2) Å revealed by X-ray diffraction analysis. Complex 3 exhibits unusual activity of nitrene transfer and C–H bond activation in comparison to the reported iron imido complexes. Specifically, the reactions of 3 with CH2=CHArCF3, an electron-deficient alkene, and CO, a strong π acid, readily afford nitrene transfer products, ArCF3CH=CHNHArTrip and ArTripNCO, respectively, yet no similar reaction occurs when 3 is treated with electron-rich alkenes and PMe3. Moreover, 3 is inert toward the weak C(sp3)–H bonds in 1,4-cyclohexadiene, THF, and toluene, whereas it can cleave the stronger C(sp)–H bond in p-trifluoromethylphenylacetylene to form an iron(II) amido alkynyl complex. Interestingly, intramolecular C(sp3)–H bond functionalization was observed by adding (p-Tol)2CN2 to 3. The unique reactivity of 3 is attributed to its low-coordinate nature and the high negative charge population on the imido N atom, which render its iron–imido unit nucleophilic in nature.

Reactivity Modes of an Iron Bis(alkoxide) Complex with Aryl Azides: Catalytic Nitrene Coupling vs Formation of Iron(III) Imido Dimers

The iron bis(alkoxide) complex Fe(OR)2(THF)2 (R = CtBu2Ph), 1, was found to have strikingly different reactivity with various aryl azides, ArN3. Azides with methyl or ethyl groups in the ortho positions of the phenyl ring react catalytically via nitrene coupling to give azoarenes, ArNNAr. Catalyst loading as low as 1 mol % yields clean, quantitative conversion of aryl azides to azoarenes at room temperature in as little as 4 h. A combination of two different aryl azides leads to the catalytic formation of all three possible azoarenes, including the asymmetric one. In contrast, reactions with aryl azides lacking ortho substituents yield stable dimeric iron imido complexes of the form (RO)(THF)Fe(μ-NAr)2Fe(THF)(OR) (Ar = 4-(trifluoromethyl)phenyl, 5; Ar = phenyl, 6; Ar = 3,5-dimethylphenyl, 7), which do not undergo catalytic nitrene coupling. The isocyanide adduct Fe(OR)2(CNR)2 (4, R = 2,6-dimethylphenyl) was obtained from the reaction of Fe(OR)2(THF)2 with two equivalents of isocyanide. No C–N bond formati...

Metal–Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands

The tris(phosphinoamide)-bridged Fe(II)Fe(II) diiron complex Fe(μ-(i)PrNPPh2)3Fe(η(2)-(i)PrNPPh2) (1) can be reduced in the absence or presence of PMe3 to generate the mixed-valence Fe(II)Fe(I) complexes Fe(μ-(i)PrNPPh2)3Fe(PPh2NH(i)Pr) (2) or Fe(μ-(i)PrNPPh2)3Fe(PMe3) (3), respectively. Following a typical oxidative group transfer procedure, treatment of 2 or 3 with organic azides generates the mixed-valent Fe(II)Fe(III) imido complexes Fe((i)PrNPPh2)3Fe≡NR (R = (t)Bu (4), Ad (5), 2,4,6-trimethylphenyl (6)). These complexes represent the first examples of first-row bimetallic complexes featuring both metal-ligand multiple bonds and metal-metal bonds. The reduced complexes 2 and 3 and imido complexes 4-6 have been characterized via X-ray crystallography, Mössbauer spectroscopy, cyclic voltammetry, and SQUID magnetometry, and a theoretical description of the bonding within these diiron complexes has been obtained using computational methods. The effect of the metal-metal interaction on the electronic structure and bonding in diiron imido complexes 4-6 is discussed in the context of similar monometallic iron imido complexes.

Dinuclear Iron–Imido Complexes with N-Heterocyclic Carbene Ligation: Synthesis, Structure, and Redox Reactivity

The introduction of an N-heterocyclic carbene ligand (NHC) to iron–imido chemistry has led to the successful preparation of a series of iron–imido complexes featuring rhombic [Fe(μ2-NDipp)2Fe]n (n = 0, 1+, 2+) cores. The dimeric iron(II)–imido complex [(IPr2Me2)Fe(μ2-NDipp)2Fe(IPr2Me2)] (1) was prepared by protonolysis of the ferrous precursor [(IPr2Me2)Fe(Mes)2] with the aniline derivative DippNH2. Complex 1 has a rhombic [Fe(μ2-NDipp)2Fe] core in which the iron sites adopt trigonal-planar geometry and have a formal Fe(II) oxidation state. Oxidation of 1 with 1 or 2 equiv of [Cp2Fe][BF4] resulted in the formation of the dinuclear iron(III) complex [F(IPr2Me2)Fe(μ2-NDipp)2Fe(IPr2Me2)F] (2) or [F(IPr2Me2)Fe(μ2-NDipp)2Fe(IPr2Me2)(BF4)] (3), respectively. However, the reaction of 1 with benzyl chloride could give either the diferric complex [Cl(IPr2Me2)Fe(μ2-NDipp)2Fe(IPr2Me2)Cl] (4) or the mixed-valent complex [(IPr2Me2)Fe(μ2-NDipp)2Fe(IPr2Me2)Cl] (5), depending on the reaction stoichiometry. Complex 5 is a...

Selectivity and Mechanism of Hydrogen Atom Transfer by an Isolable Imidoiron(III) Complex

In the literature, iron-oxo complexes have been isolated and their hydrogen atom transfer (HAT) reactions have been studied in detail. Iron-imido complexes have been isolated more recently, and the community needs experimental evaluations of the mechanism of HAT from late-metal imido species. We report a mechanistic study of HAT by an isolable iron(III) imido complex, L(Me)FeNAd (L(Me) = bulky β-diketiminate ligand, 2,4-bis(2,6-diisopropylphenylimido)pentyl; Ad = 1-adamantyl). HAT is preceded by binding of tert-butylpyridine ((t)Bupy) to form a reactive four-coordinate intermediate L(Me)Fe(NAd)((t)Bupy), as shown by equilibrium and kinetic studies. In the HAT step, very large substrate H/D kinetic isotope effects around 100 are consistent with C-H bond cleavage. The elementary HAT rate constant is increased by electron-donating groups on the pyridine additive, and by a more polar medium. When combined with the faster rate of HAT from indene versus cyclohexadiene, this trend is consistent with H(+) transfer character in the HAT transition state. The increase in HAT rate in the presence of (t)Bupy may be explained by a combination of electronic (weaker Fe=N π-bonding) and thermodynamic (more exothermic HAT) effects. Most importantly, HAT by these imido complexes has a strong dependence on the size of the hydrocarbon substrate. This selectivity comes from steric hindrance by the spectator ligands, a strategy that has promise for controlling the regioselectivity of these C-H bond activation reactions.

Catalytic C−H Bond Amination from High-Spin Iron Imido Complexes

Dipyrromethene ligand scaffolds were synthesized bearing large aryl (2,4,6-Ph(3)C(6)H(2), abbreviated Ar) or alkyl ((t)Bu, adamantyl) flanking groups to afford three new disubstituted ligands ((R)L, 1,9-R(2)-5-mesityldipyrromethene, R=aryl, alkyl). While high-spin (S=2), four-coordinate iron complexes of the type ((R)L)FeCl(solv) were obtained with the alkyl-substituted ligand varieties (for R=(t)Bu, Ad and solv=THF, OEt(2)), use of the sterically encumbered aryl-substituted ligand precluded binding of solvent and cleanly afforded a high-spin (S=2), three-coordinate complex of the type ((Ar)L)FeCl. Reaction of ((Ad)L)FeCl(OEt(2)) with alkyl azides resulted in the catalytic amination of C-H bonds or olefin aziridination at room temperature. Using a 5% catalyst loading, 12 turnovers were obtained for the amination of toluene as a substrate, while greater than 85% of alkyl azide was converted to the corresponding aziridine employing styrene as a substrate. A primary kinetic isotope effect of 12.8(5) was obtained for the reaction of ((Ad)L)FeCl(OEt(2)) with adamantyl azide in an equimolar toluene/toluene-d(8) mixture, consistent with the amination proceeding through a hydrogen atom abstraction, radical rebound type mechanism. Reaction of p-(t)BuC(6)H(4)N(3) with ((Ar)L)FeCl permitted isolation of a high-spin (S=2) iron complex featuring a terminal imido ligand, ((Ar)L)FeCl(N(p-(t)BuC(6)H(4))), as determined by (1)H NMR, X-ray crystallography, and (57)Fe Mössbauer spectroscopy. The measured Fe-N(imide) bond distance (1.768(2) Å) is the longest reported for Fe(imido) complexes in any geometry or spin state, and the disruption of the bond metrics within the imido aryl substituent suggests delocalization of a radical throughout the aryl ring. Zero-field (57)Fe Mössbauer parameters obtained for ((Ar)L)FeCl(N(p-(t)BuC(6)H(4))) suggest a Fe(III) formulation and are nearly identical with those observed for a structurally similar, high-spin Fe(III) complex bearing the same dipyrromethene framework. Theoretical analyses of ((Ar)L)FeCl(N(p-(t)BuC(6)H(4))) suggest a formulation for this reactive species to be a high-spin Fe(III) center antiferromagnetically coupled to an imido-based radical (J = -673 cm(-1)). The terminal imido complex was effective for delivering the nitrene moiety to both C-H bond substrates (42% yield) as well as styrene (76% yield). Furthermore, a primary kinetic isotope effect of 24(3) was obtained for the reaction of ((Ar)L)FeCl(N(p-(t)BuC(6)H(4))) with an equimolar toluene/toluene-d(8) mixture, consistent with the values obtained in the catalytic reaction. This commonality suggests the isolated high-spin Fe(III) imido radical is a viable intermediate in the catalytic reaction pathway. Given the breadth of iron imido complexes spanning several oxidation states (Fe(II)-Fe(V)) and several spin states (S=0→(3)/(2)), we propose the unusual electronic structure of the described high-spin iron imido complexes contributes to the observed catalytic reactivity.

Three-Coordinate Terminal Imidoiron(III) Complexes: Structure, Spectroscopy, and Mechanism of Formation

Reaction of 1-adamantyl azide with iron(I) diketiminate precursors gives metastable but isolable imidoiron(III) complexes LFe=NAd (L = bulky beta-diketiminate ligand; Ad = 1-adamantyl). This paper addresses (1) the spectroscopic and structural characterization of the Fe=N multiple bond in these interesting three-coordinate iron imido complexes, and (2) the mechanism through which the imido complexes form. The iron(III) imido complexes have been examined by (1)H NMR and electron paramagnetic resonance (EPR) spectroscopies and temperature-dependent magnetic susceptibility (SQUID), and structurally characterized by crystallography and/or extended X-ray absorption fine structure (EXAFS) measurements. These data show that the imido complexes have quartet ground states and short (1.68 +/- 0.01 A) iron-nitrogen bonds. The formation of the imido complexes proceeds through unobserved iron-N(3)R intermediates, which are indicated by QM/MM computations to be best described as iron(II) with an N(3)R radical anion. The radical character on the organoazide bends its NNN linkage to enable easy N(2) loss and imido complex formation. The product distribution between imidoiron(III) products and hexazene-bridged diiron(II) products is solvent-dependent, and the solvent dependence can be explained by coordination of certain solvents to the iron(I) precursor prior to interaction with the organoazide.