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1.
J Am Chem Soc ; 142(23): 10255-10260, 2020 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-32412757

RESUMO

Earlier work revealed that metal-superoxo species primarily function as radicals and/or electrophiles. Herein, we present ambiphilicity of a MnIII-superoxo complex revealed by its proton- and metal-coupled electron-transfer processes. Specifically, a MnIV-hydroperoxo intermediate, [Mn(BDPBrP)(OOH)]+ (1, H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) was generated by treatment of a MnIII-superoxo complex, Mn(BDPBrP)(O2•) (2) with trifluoroacetic acid at -120 °C. Detailed insights into the electronic structure of 1 are obtained using resonance Raman and multi-frequency electron paramagnetic resonance spectroscopies coupled with density functional theory calculations. Similarly, the reaction of 2 with scandium(III) triflate was shown to give a Mn(IV)/Sc(III) bridging peroxo species, [Mn(BDPBrP)(OO)Sc(OTf)n](3-n)+ (4). Furthermore, it is found that deprotonation of 1 quantitatively regenerates 2, and that one-electron oxidation of the corresponding MnIII-hydroperoxo species, Mn(BDPBrP)(OOH) (3), also yields 1.

2.
J Am Chem Soc ; 142(13): 5924-5928, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-32168447

RESUMO

In soluble methane monooxygenase enzymes (sMMO), dioxygen (O2) is activated at a diiron(II) center to form an oxodiiron(IV) intermediate Q that performs the challenging oxidation of methane to methanol. An analogous mechanism of O2 activation at mono- or dinuclear iron centers is rare in the synthetic chemistry. Herein, we report a mononuclear non-heme iron(II)-cyclam complex, 1-trans, that activates O2 to form the corresponding iron(IV)-oxo complex, 2-trans, via a mechanism reminiscent of the O2 activation process in sMMO. The conversion of 1-trans to 2-trans proceeds via the intermediate formation of an iron(III)-superoxide species 3, which could be trapped and spectroscopically characterized at -50 °C. Surprisingly, 3 is a stronger oxygen atom transfer (OAT) agent than 2-trans; 3 performs OAT to 1-trans or PPh3 to yield 2-trans quantitatively. Furthermore, 2-trans oxidizes the aromatic C-H bonds of 2,6-di-tert-butylphenol, which, together with the strong OAT ability of 3, represents new domains of oxoiron(IV) and superoxoiron(III) reactivities.

3.
Inorg Chem ; 2020 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-31990534

RESUMO

Iron complexes supported by novel π-acidic bis(imino)pyrazine (PPzDI) ligands can be functionalized at the nonligated nitrogen atom, and this has a marked effect on the redox properties of the resulting complexes. Dearomatization is observed in the presence of cobaltocene, which reversibly reduces the pyrazine core and not the imine functionality, as observed in the case of the pyridinediimine-ligated iron analogues. The resulting ligand-based radical is prone to dimerization through the formation of a long carbon-carbon bond, which can be subsequently cleaved under mild oxidative conditions.

4.
Chemistry ; 26(21): 4766-4779, 2020 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-31826307

RESUMO

X-ray structures of the halo-substituted complexes [FeIII (5-X-salMeen)2 ]ClO4 (X=F, Cl, Br, I) [salMeen=N-methyl-N-(2-aminoethyl)salicylaldiminate]at RT have revealed the presence of two discrete HS complex cations in the crystallographic asymmetric unit with two perchlorate counter ions linking them by N-Hamine ⋅⋅⋅Operchlorate interactions. At 90 K, the two complex cations are distinctly HS and LS, a rare crystallographic observation of this coexistence in the FeIII -salRen (R=alkyl) spin-crossover (SCO) system. At both temperatures, crystal packing shows dimerization through C-Himine ⋅⋅⋅Ophenolate interactions, a key feature for SCO cooperativity. Moreover, there are noncovalent contacts between the complex cations through type-II halogen-halogen bonds, which are novel in this system. The magnetic profiles and Mössbauer spectra concur with the structural analyses and reveal 50 % SCO of the type [HS-HS]↔[HS-LS] with a broad plateau. In contrast, [FeIII (5-Cl-salMeen)2 ]BPh4 ⋅2MeOH is LS and exhibits a temperature-dependent crystallographic phase transition, exemplifying the influence of lattice solvents and counter ions on SCO.

5.
J Am Chem Soc ; 142(4): 1864-1870, 2020 Jan 29.
Artigo em Inglês | MEDLINE | ID: mdl-31884789

RESUMO

Single-crystal cryogenic X-ray diffraction at 6 K, electron paramagnetic resonance spectroscopy, and correlated electronic structure calculations are combined to shed light on the nature of the metal-tris(aryloxide) and η2-H, C metal-alkane interactions in the [((t·BuArO)3tacn)UIII(Mecy-C6)]·(Mecy-C6) adduct. An analysis of the ligand field experienced by the uranium center using ab initio ligand field theory in combination with the angular overlap model yields rather unusual U-OArO and U-Ntacn bonding parameters for the metal-tris(aryloxide) interaction. These parameters are incompatible with the concept of σ and π metal-ligand overlap. For that reason, it is deduced that metal-ligand bonding in the [((t·BuArO)3tacn)UIII] moiety is predominantly ionic. The bonding interaction within the [((t·BuArO)3tacn)UIII] moiety is shown to be dispersive in nature and essentially supported by the upper-rim tBu groups of the (t·BuArO)3tacn3- ligand. Our findings indicate that the axial alkane molecule is held in place by the guest-host effect rather than direct metal-alkane ionic or covalent interactions.

6.
J Am Chem Soc ; 141(43): 17217-17235, 2019 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-31566964

RESUMO

Iron-nitrosyls have fascinated chemists for a long time due to the noninnocent nature of the NO ligand that can exist in up to five different oxidation and spin states. Coordination to an open-shell iron center leads to complex electronic structures, which is the reason Enemark-Feltham introduced the {Fe-NO}n notation. In this work, we succeeded in characterizing a series of {Fe-NO}6-9 complexes, including a reactive {Fe-NO}10 intermediate. All complexes were synthesized with the tris-N-heterocyclic carbene ligand tris[2-(3-mesitylimidazol-2-ylidene)ethyl]amine (TIMENMes), which is known to support iron in high and low oxidation states. Reaction of NOBF4 with [(TIMENMes)Fe]2+ resulted in formation of the {Fe-NO}6 compound [(TIMENMes)Fe(NO)(CH3CN)](BF4)3 (1). Stepwise chemical reduction with Zn, Mg, and Na/Hg leads to the isostructural series of high-spin iron nitrosyl complexes {Fe-NO}7,8,9 (2-4). Reduction of {Fe-NO}9 with Cs electride finally yields the highly reduced {Fe-NO}10 intermediate, key to formation of [Cs(crypt-222)][(TIMENMes)Fe(NO)], (5) featuring a metalacyclic [Fe-(NO-NHC)3-] nitrosoalkane unit. All complexes were characterized by single-crystal XRD analyses, temperature and field-dependent SQUID magnetization methods, as well as 57Fe Mössbauer, IR, UV/vis, multinuclear NMR, and dual-mode EPR spectroscopy. Spectroscopy-based DFT analyses provide insight into the electronic structures of all compounds and allowed assignments of oxidation states to iron and NO ligands. An alternative synthesis to the {Fe-NO}8 complex was found via oxygenation of the nitride complex [(TIMENMes)Fe(N)](BF4). Surprisingly, the resulting {Fe-NO}8 species is electronically and structural similar to the [(TIMENMes)Fe(N)]+ precursor. Based on the structural and electronic similarities between this nitrosyl/nitride complex couple, we adopted the strategy, developed by Wieghardt et al., of extending the Enemark-Feltham nomenclature to nitrido complexes, rendering [(TIMENMes)Fe(N)]+ as a {Fe-N}8 species.

7.
Nat Chem ; 11(11): 1019-1025, 2019 11.
Artigo em Inglês | MEDLINE | ID: mdl-31611632

RESUMO

Iron-sulfur clusters are emerging as reactive sites for the reduction of small-molecule substrates. However, the four-coordinate iron sites of typical iron-sulfur clusters rarely react with substrates, implicating three-coordinate iron. This idea is untested because fully sulfide-coordinated three-coordinate iron is unprecedented. Here we report a new type of [4Fe-3S] cluster that features an iron centre with three bonds to sulfides, and characterize examples of the cluster in three oxidation levels using crystallography, spectroscopy, and ab initio calculations. Although a high-spin electronic configuration is characteristic of other iron-sulfur clusters, the three-coordinate iron centre in these clusters has a surprising low-spin electronic configuration due to the planar geometry and short Fe-S bonds. In a demonstration of biomimetic reactivity, the [4Fe-3S] cluster reduces hydrazine, a natural substrate of nitrogenase. The product is the first example of NH2 bound to an iron-sulfur cluster. Our results demonstrate that three-coordinate iron supported by sulfide donors is a plausible precursor to reactivity in iron-sulfur clusters like the FeMoco of nitrogenase.


Assuntos
Materiais Biomiméticos/química , Compostos Ferrosos/química , Proteínas com Ferro-Enxofre/química , Materiais Biomiméticos/metabolismo , Compostos Ferrosos/metabolismo , Proteínas com Ferro-Enxofre/síntese química , Proteínas com Ferro-Enxofre/metabolismo , Modelos Moleculares , Conformação Molecular , Teoria Quântica
8.
Inorg Chem ; 58(19): 12873-12887, 2019 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-31525895

RESUMO

The vibrational properties of spin-crossover complexes [Fe(H2B(pz)2)2(L)] (pz = pyrazole) containing L = 2,2'-bipyridine (bipy) and 1,10-phenanthroline (phen) ligands are investigated by temperature-dependent infrared and Raman spectroscopy. For comparison, the analogous cobalt(II) complexes [Co(H2B(pz)2)2(L)] (L = bipy and phen) and iron(II) compounds with L = 4,4'-dimethyl-2,2'-bipyridine and 4,7-dimethyl-1,10-phenanthroline coligands are studied. Highly intense, structured bands (giant Raman features, GRFs) are observed in the resonance Raman spectra of all Fe(II) complexes between 400 and 500 cm-1 at low temperatures in the HS state which, for the SCO complexes, is excited by the Raman laser. On the basis of magnetic field Mössbauer and saturation magnetization data electronic Raman effects are excluded to account for these features. Furthermore, detailed vibrational analysis also allows excluding a vibrational resonance Raman effect involving one of the modes of the individual complexes as a possible origin of the GRFs. Consequently, these features are attributed to coherent two-phonon excitation of metal-ligand stretching vibrations in molecular dimers coupled by π-π stacking interactions.

9.
Angew Chem Int Ed Engl ; 58(49): 17589-17593, 2019 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-31532866

RESUMO

Terminal metal nitrides have been proposed as key intermediates in a series of pivotal chemical transformations. However, exploring the chemical activity of transient tetragonal iron(V) nitrides is largely impeded by their facile dimerization in fluid solutions. Herein, in situ EPR and Mössbauer investigations are presented of unprecedented oxygenation of a paramagnetic iron(V) nitrido intermediate, [FeV N(cyclam-ac)]+ (2, cyclam-ac- =1,4,8,11-tetraazacyclotetradecane-1-acetate anion), yielding an iron nitrosyl complex, [Fe(NO)(cyclam-ac)]+ (3). Further theoretical studies suggest that during the reaction a closed-shell singlet O atom is transferred to 2. Consequently, the N-O bond formation does not follow a radical coupling mechanism proposed for the N-N bond formation but is accomplished by three mutual electron-transfer pathways between 2 and the O atom donor, thanks to the ambiphilic nature of 2.

10.
Inorg Chem ; 58(18): 12365-12376, 2019 Sep 16.
Artigo em Inglês | MEDLINE | ID: mdl-31441651

RESUMO

Mo nitrogenase (N2ase) utilizes a two-component protein system, the catalytic MoFe and its electron-transfer partner FeP, to reduce atmospheric dinitrogen (N2) to ammonia (NH3). The FeMo cofactor contained in the MoFe protein serves as the catalytic center for this reaction and has long inspired model chemistry oriented toward activating N2. This field of chemistry has relied heavily on the detailed characterization of how Mo N2ase accomplishes this feat. Understanding the reaction mechanism of Mo N2ase itself has presented one of the most challenging problems in bioinorganic chemistry because of the ephemeral nature of its catalytic intermediates, which are difficult, if not impossible, to singly isolate. This is further exacerbated by the near necessity of FeP to reduce native MoFe, rendering most traditional means of selective reduction inept. We have now investigated the first fundamental intermediate of the MoFe catalytic cycle, E1, as prepared both by low-flux turnover and radiolytic cryoreduction, using a combination of Mo Kα high-energy-resolution fluorescence detection and Fe K-edge partial-fluorescence-yield X-ray absorption spectroscopy techniques. The results demonstrate that the formation of this state is the result of an Fe-centered reduction and that Mo remains redox-innocent. Furthermore, using Fe X-ray absorption and 57Fe Mössbauer spectroscopies, we correlate a previously reported unique species formed under cryoreducing conditions to the natively formed E1 state through annealing, demonstrating the viability of cryoreduction in studying the catalytic intermediates of MoFe.

11.
Inorg Chem ; 58(15): 9756-9765, 2019 Aug 05.
Artigo em Inglês | MEDLINE | ID: mdl-31328507

RESUMO

Metal-superoxo species are typically proposed as key intermediates in the catalytic cycle of dioxygen activation by metalloenzymes involving different transition metal cofactors. In this regard, while a series of Fe-, Co-, and Ni-superoxo complexes have been reported to date, well-defined Mn-superoxo complexes remain rather rare. Herein, we report two mononuclear MnIII-superoxo species, Mn(BDPP)(O2•-) (2, H2BDPP = 2,6-bis((2-(S)-diphenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) and Mn(BDPBrP)(O2•-) (2', H2BDPBrP = 2,6-bis((2-(S)-di(4-bromo)phenylhydroxyl-methyl-1-pyrrolidinyl)methyl)pyridine), synthesized by bubbling O2 into solutions of their MnII precursors, Mn(BDPP) (1) and Mn(BDPBrP) (1'), at -80 °C. A combined spectroscopic (resonance Raman and electron paramagnetic resonance (EPR) spectroscopy) and computational study evidence that both complexes contain a high-spin MnIII center (SMn = 2) antiferromagnetically coupled to a superoxo radical ligand (SOO• = 1/2), yielding an overall S = 3/2 ground state. Complexes 2 and 2' were shown to be capable of abstracting a H atom from 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPO-H) to form MnIII-hydroperoxo species, Mn(BDPP)(OOH) (5) and Mn(BDPBrP)(OOH) (5'). Complexes 5 and 5' can be independently prepared by the reactions of the isolated MnIII-aqua complexes, [Mn(BDPP)(H2O)]OTf (6) and [Mn(BDPBrP)(H2O)]OTf (6'), with H2O2 in the presence of NEt3. The parallel-mode EPR measurements established a high-spin S = 2 ground state for 5 and 5'.

12.
Inorg Chem ; 58(11): 7634-7644, 2019 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-31083985

RESUMO

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.

13.
Inorg Chem ; 58(9): 6199-6214, 2019 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-30957996

RESUMO

Previously, we reported the synthesis of Ti[N( o-(NCH2P( iPr)2)C6H4)3] and the Fe-Ti complex, FeTi[N( o-(NCH2P( iPr)2)C6H4)3], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc+), respectively. Two isostructural redox members, [FeTiL]+ and [FeTiL]- (2ox and 2red, respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL]+ complex (1ox). The solid-state structures of the [FeTiL]+/0/- series feature short metal-metal bonds, ranging from 1.94-2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57Fe Mössbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL]+,0,- series are primarily Fe-based and that the polarized Fe-Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).

14.
Inorg Chem ; 58(8): 5111-5125, 2019 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-30907584

RESUMO

In this work, a benzene-1,2-dithiolate (bdt) pentamethylcyclopentadienyl di-iron complex [Cp*Fe(µ-η2:η4-bdt)FeCp*] and its [Cp*Fe(bdt)(X)FeCp*] analogues (where X = N2H2, N2H3-, H-, NH2-, NHCH3-, or NO+) were investigated through spectroscopic and computational studies. These complexes are of relevance as model systems for dinitrogen activation in nitrogenase and share with its active site the presence of iron, sulfur ligands, and a very flexible electronic structure. On the basis of a combination of X-ray emission spectroscopy (XES), X-ray crystallography, Mössbauer, NMR, and EPR spectroscopy, the geometric and electronic structure of the series has been experimentally elucidated. All iron atoms were found to be in a local low-spin configuration. When no additional X ligand is bound, the bdt ligand is tilted and features a stabilizing π-interaction with one of the iron atoms. The number of lone-pair orbitals provided by the nitrogen-containing species is crucial to the overall electronic structure. When only one lone-pair is present and the iron atoms are bridged by one atom, a three-center bond occurs, and a direct Fe-Fe bond is absent. If the bridging atom provides two lone-pairs, then an Fe-Fe bond is formed. A recurring theme for all ligands is σ-donation into the unoccupied eg manifolds of both iron atoms and back-donation from the t2g manifolds into the ligand π* orbitals. The latter results in a weakening of the double bond of the bound ligand, and in the case of NO+, it results in a weakening of all bonds that comprise triple bond. The electron-rich thiolates further amplify this effect and can also serve as bases for proton binding. While the above observations have been made for the studied di-iron complexes, they may be of relevance for the active site in nitrogenase, where a similar N2 binding mode may occur allowing for the simultaneous weakening of the N2 σ bond and π bonds.

15.
Chem Sci ; 10(3): 918-929, 2019 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-30774886

RESUMO

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.

16.
J Am Chem Soc ; 141(6): 2421-2434, 2019 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-30620571

RESUMO

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.

17.
Angew Chem Int Ed Engl ; 57(48): 15717-15722, 2018 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-30239076

RESUMO

To probe the possibility that carbodicarbenes (CDCs) are redox active ligands, all four members of the redox series [Fe(1)2 ]n+ (n=2-5) were synthesized, where 1 is a neutral tridentate CDC. Through a combination of spectroscopy and DFT calculations, the electronic structure of the pentacation is shown to be [FeIII (1.+ )2 ]5+ (S= 1 / 2 ). That of [Fe(1)2 ]4+ is more ambiguous, but it has significant contributions from the open-shell singlet [FeIII (1)(1.+ )]4+ (S=0). The observed spin states derive from antiferromagnetic coupling of their constituent low-spin iron(III) centres and cation radical ligands. This marks the first time redox activity has been observed for carbones and expands the diverse chemical behaviour known for these ligands.

18.
Nat Commun ; 9(1): 2572, 2018 07 03.
Artigo em Inglês | MEDLINE | ID: mdl-29968702

RESUMO

Spin-phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here, we show for the first time distinct couplings of g phonons of CoII(acac)2(H2O)2 (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1-2 cm-1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. This work spectroscopically reveals and quantitates the spin-phonon couplings in typical transition metal complexes and sheds light on the origin of the spin-phonon entanglement.

19.
Inorg Chem ; 57(15): 9515-9530, 2018 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-30044087

RESUMO

Understanding the detailed electronic structure of transition metal ions is essential in numerous areas of inorganic chemistry. In particular, the ability to map out the many particle d-d spectrum of a transition metal catalyst is key to understanding and predicting reactivity. However, from a practical perspective, there are often experimental limitations on the ability to determine the energetic ordering, and multiplicity of all the excited states. These limitations derive in part from parity and spin-selection rules, as well as from the limited energy range of many standard laboratory instruments. Herein, we demonstrate the ability of 2p3d resonant inelastic X-ray scattering (RIXS) to obtain detailed insights into the many particle spectrum of simple inorganic molecular iron complexes. The present study focuses on low-spin ferrous and ferric iron complexes, including [FeIII/II(tacn)2]3+/2+ and [FeIII/II(CN)6]3-/4-. This series thus allows us to assess the contribution of d-count and ligand donor type, by comparing the purely σ-donating tacn ligand to the π-accepting cyanide. In order to highlight the conceptual difference between RIXS and traditional optical spectroscopy, we compare first RIXS results with UV-vis and magnetic circular dichroism spectroscopy. We then highlight the ability of 2p3d RIXS to (1) separate d-d transitions from charge transfer transitions and (2) to determine the many particle d-d spectrum over a much wider energy range than is possible by optical spectroscopy. Our experimental results are correlated with semiempirical multiplet simulations and ab initio complete active space self-consistent field calculations in order to obtain detailed assignments of the excited states. These results show that Δ S = 1, and possibly Δ S = 2, transitions may be observed in 2p3d RIXS spectra. Hence, this methodology has great promise for future applications in all areas of transition metal inorganic chemistry.

20.
J Am Chem Soc ; 140(30): 9531-9544, 2018 08 01.
Artigo em Inglês | MEDLINE | ID: mdl-29984578

RESUMO

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.

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