Deciphering the Origin of Regioselectivity in Ru(II)-Catalyzed C-H Annulation of N-Chlorobenzamides with 1,3-Diynes.

Understanding the reaction mechanism and origin of regioselectivity in transition metal-catalyzed C-H activation/annulation reactions with 1,3-diynes has remained an intriguing challenge. In this article, to establish the mechanism and decipher the origin of regioselectivity, we report a detailed computational density functional theory-based mechanistic investigation on the recently developed Ru(II)-catalyzed [4 + 2] annulation of N-chlorobenzamides with 1,3-diynes for the synthesis of 3-alkynylated isoquinolone derivatives. Our calculations reveal a redox-neutral pathway for the annulation reaction. The stepwise analysis of the reaction channels indicates the migratory insertion step and the concerted reductive elimination/oxidative addition of the Ru(p-cymene) moiety to form the N-C bond leading to the 3-alkynylated product to be the selectivity- and rate-determining steps, respectively. Finally, the distortion/interaction analysis using the activation-strain model suggests the steric effect as the determining factor for the observed regioselectivity for the formation of the 3-alkynylated product. Overall, the computationally obtained key insights into the catalytic mechanism and the origin of regioselectivity in the C-H activation/annulation reaction can be used as a guide to rationally design and develop novel transformation strategies for heterocycle synthesis.

ColPTMScape: An open access knowledge base for tissue-specific collagen PTM maps.

Collagen is a key component of the extracellular matrix (ECM). In the remodeling of ECM, a remarkable variation in collagen post-translational modifications (PTMs) occurs. This makes collagen a potential target for understanding extracellular matrix remodeling during pathological conditions. Over the years, scientists have gathered a huge amount of data about collagen PTM during extracellular matrix remodeling. To make such information easily accessible in a consolidated space, we have developed ColPTMScape (https://colptmscape.iitmandi.ac.in/), a dedicated knowledge base for collagen PTMs. The identified site-specific PTMs, quantitated PTM sites, and PTM maps of collagen chains are deliverables to the scientific community, especially to matrix biologists. Through this knowledge base, users can easily gain information related to the difference in the collagen PTMs across different tissues in different organisms.

Enantioselective Amination of 3-Substituted-2-benzofuranones via Non-covalent N-Heterocyclic Carbene Catalysis.

Herein, an efficient method for asymmetric α-amination of 2-benzofuranones with N-heterocyclic carbene (NHC) catalysis is reported. The process is based on non-covalent interaction of NHC with substrate, facilitating the formation of a chiral ion-pair that encompasses enolate and azolium salt. The activated enolate adds to an electrophilic amine source with sufficient facial control to furnish an enantioenriched product having an amine substituted quaternary stereocenter. The process displays a broad substrate scope. A preparative scale synthesis has been achieved. Preliminary mechanistic investigations based on experimental and DFT studies suggest a reaction pathway that involves non-covalent substrate/NHC interactions and essentially implicate the role of π-π interaction in diastereomeric transition states for stereo-chemical discrimination.

How Axial Coordination Regulates the Electronic Structure and C-H Amination Reactivity of Fe-Porphyrin-Nitrene?

Detailed electronic structure and its correlation with the intramolecular C-H amination reactivity of Fe-porphyrin-nitrene intermediates bearing different "axial" coordination have been investigated using multiconfigurational complete active space self-consistent field (CASSCF), N-electron valence perturbation theory (NEVPT2), and hybrid density functional theory (DFT-B3LYP) calculations. Three types of "axial" coordination, -OMe/-O(H)Me (1-Sul/2-Sul), -SMe/-S(H)Me (3-Sul/4-Sul), and -NMeIm (MeIm = 3-methyl-imidazole) (5-Sul) mimicking serine, cysteine, and histidine, respectively, along with no axial coordination (6-Sul) have been considered to decipher how the "axial" coordination of different strengths regulates the electronic integrity of the Fe-N core and nitrene-transfer reactivity of Fe-porphyrin-nitrene intermediates. CASSCF-based natural orbitals reveal two distinct classes of electronic structures: Fe-nitrenes (1-Sul and 3-Sul) with relatively stronger axial coordination (-OMe and -SMe) display "imidyl" nature and those (2-Sul, 4-Sul, and 6-Sul) with weaker axial coordination (-O(H)Me, -S(H)Me and no axial coordination) exhibit "imido-like" character. A borderline between the two classes is also observed with NMeIm axial coordination (5-Sul). Axial coordination of different strengths not only regulates the electronic structure but also modulates the Fe-3d orbital energies, as revealed through the d-d transition energies obtained by CASSCF/NEVPT2 calculations. The relatively lower energy of Fe-3dz2 orbital allows easy access to low-lying high-spin quintet states in the cases of weaker "axial" coordination (2-Sul, 4-Sul, and 6-Sul), and the associated hydrogen atom transfer (HAT) reactivity appears to involve two-state triplet-quintet reactivity through minimum energy crossing point (3,5MECP) between the spin states. In stark contrast, Fe-nitrenes with relatively stronger "axial" coordination (1-Sul and 3-Sul) undergo triplet-only HAT reactivity. Overall, this in-depth electronic structure investigation and HAT reactivity evaluation reveal that the weaker axial coordination in Fe-porphyrin-nitrene complexes (2-Sul, 4-Sul, and 6-Sul) can promote more efficient C-H oxidation through the quintet spin state.

µ2 -η1 :η1 -N2 Bridged Bimetallic Dinitrogen Complexes: Geometry of the First Excited State in Connection to N2 π-Photoactivation.

Bimetallic end-on µ2 -η1 :η1 -N2 bridging dinitrogen complexes have served as the platform for photochemical N2 activation, mainly for the N-N cleavage. However, the alternate N-N π-photoactivation route has remained largely unexplored. This study strengthens the notion of weakening the N-N bond through the population of π* orbital upon electronic excitation from the ground to the first excited state using four prototypical complexes based on Fe (1), Mo (2), and Ru (3,4). The complexes 1-4 possess characteristic N-N π* based LUMO (π*-π*-π*) centered on their M-N-N-M core, which was earlier postulated to play a central role in the N2 photoactivation. Vertical electronic excitation of the highest oscillator strength involves transitions to the N-N π*-based acceptor orbital (π*-π*-π*) in complexes 1-4. This induces geometry relaxation of the first excited metal-to-nitrogen (π*) charge transfer (1 MNCT) state leading to a "zigzag" M-N-N-M core in the equilibrium structure. Obtaining the equilibrium geometry in the first excited state with the full-sized complexes widens the scope of N-N π-photoactivation with µ2 -η1 :η1 -N2 bridging dinitrogen complexes. Promisingly, the elongated N-N bond and bent ∠MNN angle in the photoexcited S1 state of 1-4 resemble their radical- and di-anion forms, which lead toward thermodynamically feasible N-N protonation in the S1 excited state.

Revisiting the electronic structure of N2-bound cAAC-borylene at the CASSCF level: a detailed bonding picture of borylene-N2 interaction.

A base-trapped borylene species featuring a cyclic-(alkyl)(amino)carbene (cAAC) has shown unique bonding interactions with dinitrogen, thereby, opening a new avenue for N2 activation by main-group compounds. The detailed electronic structure and qualitative bonding picture between cAAC-trapped borylene and N2 remain to be fully understood. This work presents a multiconfigurational complete active space self-consistent field (CASSCF)-based electronic structure investigation on the N2-bound cAAC-borylene species (1) isolated by Braunschweig et al. Specifically, the synergistic bonding between the borylene units and N2 involving the donation from the N-N σ to the unoccupied orbital of borylene and back-donation from the occupied orbital of borylene to the N-N π* has been unequivocally established using CASSCF-derived natural orbitals and electronic configuration. Bonding interactions between the HOMO of the borylene units and the N-N π* (HOMOcAAC-B + π*NN) and the LUMO of the borylene units and the N-N σ (LUMOcAAC-B + σNN) in 1 were apparent through the CASSCF-derived natural orbitals. The unique bonding of the B-N-N-B core in 1 and the resulting geometry have also been compared with the M-N-N-M core of a prototypical transition metal(M)-N2 complex. Finally, the change in the electronic structure and geometry of the N2-bound borylene species 1 on two-electron reduction has been investigated in the context of N2 activation.

Trinuclear PdII Complexes with a C3 -Symmetric Triethynylbenzene-Based Tris-NHC Ligand: Catalytic Benefits.

A new C3 -symmetric tris-imidazolium tribromide salt 3, featuring 1,3,5-substituted triethynylbenzene, was used for the preparation of a trinuclear PdII pyridine-enhanced precatalyst preparation stabilization and initiation-type (PEPPSI) complex by triple C2 deprotonation followed by the addition of PdCl2 . Trinuclear PdII complex possessing a combination of NHC and PPh3 ligands has also been synthesized. The corresponding mononuclear palladium(II) complexes have also been synthesized for the comparison purpose. All these complexes have been characterized by using NMR spectroscopy and ESI mass spectrometry. The molecular structure of the trinuclear palladium(II) complex bearing mixed carbene and pyridine donor ligands has been established by using single crystal XRD. All the palladium(II) complexes have been used as pre-catalysts, which gave good to excellent yields in intermolecular α-arylation of 1-methyl-2-oxindole and Sonogashira coupling reaction. Catalytic studies indicate an enhanced activity of the trinuclear PdII complex in comparison to the corresponding mononuclear PdII complex for both catalytic transformations. The better performance of the trinuclear complex has also been further supported by preliminary electrochemical measurements. A negative mercury poison test was observed for both the aforementioned catalyses and therefore, it is likely that these organic transformations proceed homogeneously.

Asymmetric Aminative Dearomatization of 2-Naphthols via Non-covalent N-Heterocyclic Carbene Catalysis.

Herein, successful utilization of non-covalent N-heterocyclic carbene (NHC) catalysis toward asymmetric aminative dearomatization of naphthols is presented. The NHC-catalyzed process offers enantioselective synthesis of cyclic enones possessing a nitrogen-containing α-quaternary stereocenter. The reaction applies to various functionalized substrates including acid-labile groups and is shown to be scalable. Substrate activation via an O-H···NHC hydrogen-bonding interaction is suggested based on the results obtained in mechanistic studies.

Origin of the Distinctive Electronic Structure of Co- and Fe-Porphyrin-Nitrene and Its Effect on Their Nitrene Transfer Reactivity.

Metal-bound nitrene species are the crucial intermediate in catalytic nitrene transfer reactions exhibited by engineered enzymes and molecular catalysts. The electronic structure of such species and its correlation with nitrene transfer reactivity have not been fully understood yet. This work presents an in-depth electronic structure analysis and nitrene transfer reactivity of two prototypical metal-nitrene species derived from CoII(TPP) and FeII(TPP) (TPP = meso-tetraphenylporphyrin) complexes and tosyl azide nitrene precursor. Parallel to the well-known "cobalt(III)-imidyl" electronic structure of the Co-porphyrin-nitrene species, the formation mechanism and electronic structure of the elusive Fe-porphyrin-nitrene have been established using density functional theory (DFT) and multiconfigurational complete active-space self-consistent field (CASSCF) calculations. Electronic structure evolution analysis for the metal-nitrene formation step and CASSCF-derived natural orbitals advocates that the electronic nature of the metal-nitrene (M-N) core of Fe(TPP) is strikingly different from that of the Co(TPP). Specifically, the "imidyl" nature of the Co-porphyrin-nitrene [(TPP)CoIII-•NTos] (Tos = tosyl) (I1Co) is contrasted by the "imido-like" character of the Fe-porphyrin-nitrene [(TPP)FeIV[Formula: see text]NTos] (I1Fe). This difference between Co- and Fe-nitrene has been attributed to the additional interactions between Fe-dπ and N-pπ orbitals in Fe-nitrene, which is further complemented by the shortened Fe-N bond length of 1.71 Å. This stronger M-N bond in Fe-nitrene compared to the Co-nitrene is also reflected in the higher exothermicity (ΔΔH = 16 kcal/mol) of the Fe-nitrene formation step. The "imido-like" character renders a relatively lower spin population on the nitrene nitrogen (+0.42) in the Fe-nitrene complex I1Fe, which undergoes the nitrene transfer to the C═C bond of styrene with a considerably higher enthalpy barrier (ΔH‡ = 10.0 kcal/mol) compared to the Co congener I1Co (ΔH‡ = 5.6 kcal/mol) possessing a higher nitrogen spin population (+0.88) and a relatively weaker M-N bond (Co-N = 1.80 Å).

A naphthalene-based heterobimetallic triazolylidene IrIII/PdII complex: regioselective to regiospecific C-H activation, tandem catalysis and a copper-free Sonogashira reaction.

Heterobimetallic complexes featuring mesoionic carbene (MIC) donor ligands are gaining enormous popularity in tandem catalysis owing to the combined action of two different metal centers during catalysis. A rare version of the heterobimetallic PdII/IrIII complex possessing a cyclometalated mesoionic carbene (MIC) ligand is presented along with the analogous homodinuclear PdII complex. A sterically controlled regiospecific cyclometalation towards the formation of a six-membered ring complex over a five-membered ring complex has been performed using a naphthalene-based bis-MIC ligand platform. The interplay between regioselective vs. regiospecific C-H bond activation for the synthesis of cyclometalated IrIII complexes has also been demonstrated using the corresponding naphthyl-derived mono-imidazolylidene ligand. Both homodinuclear PdII and heterobimetallic PdII/IrIII complexes have been characterized using standard spectroscopic techniques including 1H, 13C{1H}, 2D correlation NMR spectroscopy and ESI mass spectrometry. The structure of the cyclometalated heterobimetallic complex has been established by single crystal XRD. The heterobimetallic complex has been employed as a pre-catalyst in the tandem Suzuki-Miyaura/transfer hydrogenation reaction and the homobimetallic PdII complex has been successfully employed as a catalyst in both the Sonogashira coupling and α-arylation of 1-methyl-2-oxindole.

Cu(II)-Based Coordination Polymer as a Pristine Form Usable Electrocatalyst for Oxygen Reduction Reaction: Experimental Evaluation and Theoretical Insights into Biomimetic Mechanistic Aspects.

As the postsynthesis-processed metal-organic material-based catalysts for energy applications add additional cost to the whole process, the importance of developing synthesized usable pristine catalysts is quite evident. The present work reports a new Cu-based coordination polymer (Cu-CP) catalyst to be used in its pristine form for oxygen reduction reaction (ORR) application. The catalyst was characterized using single-crystal X-ray diffraction, field emission scanning electron microscopy, and X-ray photoemission spectroscopy. The Cu-CP exhibits admirable electrocatalytic ORR activity with an onset potential of 0.84 V versus RHE and a half wave potential of 0.69 V versus RHE. As revealed by the density functional theory-based computational mechanistic investigation of the electrocatalytic ORR process, the electrochemically reduced Cu(I) center binds to the molecular O2 through an exergonic process (ΔG = -6.8 kcal/mol) and generates the Cu(II)-O2•- superoxo intermediate. Such superoxo intermediates are frequently encountered in the catalytic cycle of the Cu-containing metalloenzymes in their O2 reduction reaction. This intermediate undergoes coupled proton and electron transfer processes to give OH- in an alkaline medium involving H2O2 as the intermediate. The electrocatalytic performance of Cu-CP remained stable even up to 3000 cycles. Overall, the newly developed Cu-CP-based electrocatalyst holds promising potential for efficient biomimetic ORR reactivity, which opens new possibilities toward the development of robust coordination polymer-based electrocatalysts.

Electrocatalytic Water Oxidation Activity of Molecular Copper Complexes: Effect of Redox-Active Ligands.

Two molecular copper(II) complexes, (NMe4)2[CuII(L1)] (1) and (NMe4)2[CuII(L2)] (2), ligated by a N2O2 donor set of ligands [L1 = N,N'-(1,2-phenylene)bis(2-hydroxy-2-methylpropanamide), and L2 = N,N'-(4,5-dimethyl-1,2-phenylene)bis(2-hydroxy-2-methylpropanamide)] have been synthesized and thoroughly characterized. An electrochemical study of 1 in a carbonate buffer at pH 9.2 revealed a reversible copper-centered redox couple at 0.51 V, followed by two ligand-based oxidation events at 1.02 and 1.25 V, and catalytic water oxidation at an onset potential of 1.28 V (overpotential of 580 mV). The electron-rich nature of the ligand likely supports access to high-valent copper species on the CV time scale. The results of the theoretical electronic structure investigation were quite consistent with the observed stepwise ligand-centered oxidation process. A constant potential electrolysis experiment with 1 reveals a catalytic current density of >2.4 mA cm-2 for 3 h. A one-electron-oxidized species of 1, (NMe4)[CuIII(L1)] (3), was isolated and characterized. Complex 2, on the contrary, revealed copper and ligand oxidation peaks at 0.505, 0.90, and 1.06 V, followed by an onset water oxidation (WO) at 1.26 V (overpotential of 560 mV). The findings show that the ligand-based oxidation reactions strongly depend upon the ligand's electronic substitution; however, such effects on the copper-centered redox couple and catalytic WO are minimal. The energetically favorable mechanism has been established through the theoretical calculation of stepwise reaction energies, which nicely explains the experimentally observed electron transfer events. Furthermore, as revealed by the theoretical calculations, the O-O bond formation process occurs through a water nucleophilic attack mechanism with an easily accessible reaction barrier. This study demonstrates the importance of redox-active ligands in the development of molecular late-transition-metal electrocatalysts for WO reactions.

Absorption and emission of light in red emissive carbon nanodots.

The structure-function relationship, especially the origin of absorption and emission of light in carbon nanodots (CNDs), has baffled scientists. The multilevel complexity arises due to the large number of by-products synthesized during the bottom-up approach. By performing systematic purification and characterization, we reveal the presence of a molecular fluorophore, quinoxalino[2,3-b]phenazine-2,3-diamine (QXPDA), in a large amount (∼80% of the total mass) in red emissive CNDs synthesized from o-phenylenediamine (OPDA), which is one of the well-known precursor molecules used for CND synthesis. The recorded NMR and mass spectra tentatively confirm the structure of QXPDA. The close resemblance of the experimental vibronic progression and the mirror symmetry of the absorption and emission spectra with the theoretically simulated spectra confirm an extended conjugated structure of QXPDA. Interestingly, QXPDA dictates the complete emission characteristics of the CNDs; in particular, it showed a striking similarity of its excitation independent emission spectra with that of the original synthesized red emissive CND solution. On the other hand, the CND like structure with a typical size of ∼4 nm was observed under a transmission electron microscope for a blue emissive species, which showed both excitation dependent and independent emission spectra. Interestingly, Raman spectroscopic data showed the similarity between QXPDA and the dot structure thus suggesting the formation of the QXPDA aggregated core structure in CNDs. We further demonstrated the parallelism in trends of absorption and emission of light from a few other red emissive CNDs, which were synthesized using different experimental conditions.

Molecular-level insights into the self-assembly driven enantioselective recognition process.

The importance of the orientation of functional groups in a chiral environment on enantioselective recognition has been demonstrated. Orientation controlled interactions of functional groups in (R)/(S)-MA lead to a visually differentiable morphology with an arginine-based gelator. The crucial role of various molecular-level interactions discriminating the enantioselective self-assembly has been established using different analytical techniques, crystal structure analysis, and DFT calculations.

Hydrogen-Bonding Assisted Catalytic Kinetic Resolution of Acyclic ß-Hydroxy Amides.

Enantioenriched acyclic α-substituted ß-hydroxy amides are valuable compounds in chemical, material and medicinal sciences, but their enantioselective synthesis remains challenging. A catalytic kinetic resolution (KR) of such amides with selectivity factor(s) up to >200 is developed via enantioselective acylation of primary alcohol with N-heterocyclic carbene. An enhanced selectivity for the catalytic KR process is realized using cyclic tertiary amine as base additive. Diastereomeric transition state models for the process are proposed to rationalize the origin of enantioselectivity.

Computational mechanistic insights into non-noble-metal-catalysed CO2 conversion.

The conversion of CO2 into liquid fuels and value-added fine chemicals is of significant interest for both the environment and the global energy demand. In this frontier article, we highlight viable methods for transforming CO2 into valuable C1 feedstocks and summarize the key mechanistic aspects obtained by in-depth computational investigations of three important pathways of two-electron CO2 reduction: (i) CO2 dissociation to CO (ii) CO2 dimerization to CO32- and CO, and (iii) CO2 hydrogenation to formate. Lastly, we present our outlook on how theoretically obtained mechanistic insights could be translated into strategies for designing efficient non-noble-metal catalysts for CO2 reduction.

Reduction of CO2 by a masked two-coordinate cobalt(i) complex and characterization of a proposed oxodicobalt(ii) intermediate.

Fixation and chemical reduction of CO2 are important for utilization of this abundant resource, and understanding the detailed mechanism of C-O cleavage is needed for rational development of CO2 reduction methods. Here, we describe a detailed analysis of the mechanism of the reaction of a masked two-coordinate cobalt(i) complex, L tBuCo (where L tBu = 2,2,6,6-tetramethyl-3,5-bis[(2,6-diisopropylphenyl)imino]hept-4-yl), with CO2, which yields two products of C-O cleavage, the cobalt(i) monocarbonyl complex L tBuCo(CO) and the dicobalt(ii) carbonate complex (L tBuCo)2(µ-CO3). Kinetic studies and computations show that the κN,η6-arene isomer of L tBuCo rearranges to the κ2 N,N' binding mode prior to binding of CO2, which contrasts with the mechanism of binding of other substrates to L tBuCo. Density functional theory (DFT) studies show that the only low-energy pathways for cleavage of CO2 proceed through bimetallic mechanisms, and DFT and highly correlated domain-based local pair natural orbital coupled cluster (DLPNO-CCSD(T)) calculations reveal the cooperative effects of the two metal centers during facile C-O bond rupture. A plausible intermediate in the reaction of CO2 with L tBuCo is the oxodicobalt(ii) complex L tBuCoOCoL tBu, which has been independently synthesized through the reaction of L tBuCo with N2O. The rapid reaction of L tBuCoOCoL tBu with CO2 to form the carbonate product indicates that the oxo species is kinetically competent to be an intermediate during CO2 cleavage by L tBuCo. L tBuCoOCoL tBu is a novel example of a thoroughly characterized molecular cobalt-oxo complex where the cobalt ions are clearly in the +2 oxidation state. Its nucleophilic reactivity is a consequence of high charge localization on the µ-oxo ligand between two antiferromagnetically coupled high-spin cobalt(ii) centers, as characterized by DFT and multireference complete active space self-consistent field (CASSCF) calculations.

Electron Paramagnetic Resonance Signature of Tetragonal Low Spin Iron(V)-Nitrido and -Oxo Complexes Derived from the Electronic Structure Analysis of Heme and Non-Heme Archetypes.

Iron(V)-nitrido and -oxo complexes have been proposed as key intermediates in a diverse array of chemical transformations. Herein we present a detailed electronic-structure analysis of [FeV(N)(TPP)] (1, TPP2- = tetraphenylporphyrinato), and [FeV(N)(cyclam-ac)]+ (2, cyclam-ac = 1,4,8,11-tetraazacyclotetradecane-1-acetato) using electron paramagnetic resonance (EPR) and 57Fe Mössbauer spectroscopy coupled with wave function based complete active-space self-consistent field (CASSCF) calculations. The findings were compared with all other well-characterized genuine iron(V)-nitrido and -oxo complexes, [FeV(N)(MePy2tacn)](PF6)2 (3, MePy2tacn = methyl- N', N″-bis(2-picolyl)-1,4,7-triazacyclononane), [FeV(N){PhB( t-BuIm)3}]+ (4, PhB(tBuIm)3- = phenyltris(3- tert-butylimidazol-2-ylidene)borate), and [FeV(O)(TAML)]- (5, TAML4- = tetraamido macrocyclic ligand). Our results revealed that complex 1 is an authenticated iron(V)-nitrido species and contrasts with its oxo congener, compound I, which contains a ferryl unit interacting with a porphyrin radical. More importantly, tetragonal iron(V)-nitrido and -oxo complexes 1-3 and 5 all possess an orbitally nearly doubly degenerate S = 1/2 ground state. Consequently, analogous near-axial EPR spectra with g|| < g⊥ ≤ 2 were measured for them, and their g|| and g⊥ values were found to obey a simple relation of g⊥2 + (2 - g∥)2 = 4. However, the bonding situation for trigonal iron(V)-nitrido complex 4 is completely different as evidenced by its distinct EPR spectrum with g|| < 2 < g⊥. Further in-depth analyses suggested that tetragonal low spin iron(V)-nitrido and -oxo complexes feature electronic structures akin to those found for complexes 1-3 and 5. Therefore, the characteristic EPR signals determined for 1-3 and 5 can be used as a spectroscopic marker to identify such highly reactive intermediates in catalytic processes.

Electronic Structure Contributions of Non-Heme Oxo-Iron(V) Complexes to the Reactivity.

Oxo-iron(V) species have been implicated in the catalytic cycle of the Rieske dioxygenase. Their synthetic analog, [FeV(O)(OC(O)CH3)(PyNMe3)]2+ (1, PyNMe3 = 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9-trimethyl), derived from the O-O bond cleavage of its acetylperoxo iron(III) precursor, has been shown experimentally to perform regio- and stereoselective C-H and C═C bond functionalization. However, its structure-activity relation is poorly understood. Herein we present a detailed electronic-structure and spectroscopic analysis of complex 1 along with well-characterized oxo-iron(V) complexes, [FeV(O)(TAML)]- (2, TAML = tetraamido macrocyclic ligand), [FeV(O)(TMC)(NC(O)CH3)]+ (4, TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), and [FeV(O)(TMC)(NC(OH)CH3)]2+ (4-H+), using wave function-based multireference complete active-space self-consistent field calculations. Our results reveal that the x/ y anisotropy of the 57Fe A-matrix is not a reliable spectroscopic marker to identify oxo-iron(V) species and that the drastically different A x and A y values determined for complexes 1, 4, and 4-H+ have distinctive origins compared to complex 2, a genuine oxo-iron(V) species. Complex 1, in fact, has a dominant character of [FeIV(O···OC(O)CH3)2-•]2+, i.e., an SFe = 1 iron(IV) center antiferromagnetically coupled to an O-O σ* radical, where the O-O bond has not been completely broken. Complex 4 is best described as a triplet ferryl unit that strongly interacts with the trans acetylimidyl radical in an antiferromagnetic fashion, [FeIV(O)(•N═C(O-)CH3)]+. Complex 4-H+ features a similar electronic structure, [FeIV(O)(•N═C(OH)CH3)]2+. Owing to the remaining approximate half σ-bond in the O-O moiety, complex 1 can arrange two electron-accepting orbitals (α σ*O-O and ß Fe-d xz) in such a way that both orbitals can simultaneously interact with the doubly occupied electron-donating orbitals (σC-H or πC-C). Hence, complex 1 can promote a concerted yet asynchronous two-electron oxidation of the C-H and C═C bonds, which nicely explains the stereospecificity observed for complex 1 and the related species.

Nonclassical Single-State Reactivity of an Oxo-Iron(IV) Complex Confined to Triplet Pathways.

C-H bond activation mediated by oxo-iron (IV) species represents the key step of many heme and nonheme O2-activating enzymes. Of crucial interest is the effect of spin state of the FeIV(O) unit. Here we report the C-H activation kinetics and corresponding theoretical investigations of an exclusive tetracarbene ligated oxo-iron(IV) complex, [LNHCFeIV(O)(MeCN)]2+ (1). Kinetic traces using substrates with bond dissociation energies (BDEs) up to 80 kcal mol-1 show pseudo-first-order behavior and large but temperature-dependent kinetic isotope effects (KIE 32 at -40 °C). When compared with a topologically related oxo-iron(IV) complex bearing an equatorial N-donor ligand, [LTMCFeIV(O) (MeCN)]2+ (A), the tetracarbene complex 1 is significantly more reactive with second order rate constants k'2 that are 2-3 orders of magnitude higher. UV-vis experiments in tandem with cryospray mass spectrometry evidence that the reaction occurs via formation of a hydroxo-iron(III) complex (4) after the initial H atom transfer (HAT). An extensive computational study using a wave function based multireference approach, viz. complete active space self-consistent field (CASSCF) followed by N-electron valence perturbation theory up to second order (NEVPT2), provided insight into the HAT trajectories of 1 and A. Calculated free energy barriers for 1 reasonably agree with experimental values. Because the strongly donating equatorial tetracarbene pushes the Fe-dx2-y2 orbital above dz2, 1 features a dramatically large quintet-triplet gap of ∼18 kcal/mol compared to ∼2-3 kcal/mol computed for A. Consequently, the HAT process performed by 1 occurs on the triplet surface only, in contrast to complex A reported to feature two-state-reactivity with contributions from both triplet and quintet states. Despite this, the reactive FeIV(O) units in 1 and A undergo the same electronic-structure changes during HAT. Thus, the unique complex 1 represents a pure "triplet-only" ferryl model.