A Bioinspired Nonheme FeIII-(O22-)-CuII Complex with an St = 1 Ground State.

Cytochrome c oxidase (CcO) is a heme copper oxidase (HCO) that catalyzes the natural reduction of oxygen to water. A profound understanding of some of the elementary steps leading to the intricate 4e-/4H+ reduction of O2 is presently lacking. A total spin St = 1 FeIII-(O22-)-CuII (IP) intermediate is proposed to reduce the overpotentials associated with the reductive O-O bond rupture by allowing electron transfer from a tyrosine moiety without the necessity of any spin-surface crossing. Direct evidence of the involvement of IP in the CcO catalytic cycle is, however, missing. A number of heme copper peroxido complexes have been prepared as synthetic models of IP, but all of them possess the catalytically nonrelevant St = 0 ground state resulting from antiferromagnetic coupling between the S = 1/2 FeIII and CuII centers. In a complete nonheme approach, we now report the spectroscopic characterization and reactivity of the FeIII-(O22-)-CuII intermediates 1 and 2, which differ only by a single -CH3 versus -H substituent on the central amine of the tridentate ligands binding to copper. Complex 1 with an end-on peroxido core and ferromagnetically (St = 1) coupled FeIII and CuII centers performs H-bonding-mediated O-O bond cleavage in the presence of phenol to generate oxoiron(IV) and exchange-coupled copper(II) and PhO• moieties. In contrast, the µ-η2:η1 peroxido complex 2, with a St = 0 ground state, is unreactive toward phenol. Thus, the implications for spin topology contributions to O-O bond cleavage, as proposed for the heme FeIII-(O22-)-CuII intermediate in CcO, can be extended to nonheme chemistry.

Trapping of a phenoxyl radical at a non-haem high-spin iron(II) centre.

The activation of dioxygen at haem and non-haem metal centres, and subsequent functionalization of unactivated C‒H bonds, has been a focal point of much research. In iron-mediated oxidation reactions, O2 binding at an iron(II) centre is often accompanied by an oxidation of the iron centre. Here we demonstrate dioxygen activation by sodium tetraphenylborate and protons in the presence of an iron(II) complex to form a reactive radical species, whereby the iron oxidation state remains unaltered in the presence of a highly oxidizing phenoxyl radical and O2. This complex, containing an unusual iron(II)-phenoxyl radical motif, represents an elusive example of a spectroscopically characterized oxygen-derived iron(II)-reactive intermediate during chemical and biological dioxygen activation at haem and non-haem iron active centres. The present report opens up strategies for the stabilization of a phenoxyl radical cofactor, with its full oxidizing capabilities, to act as an independent redox centre next to an iron(II) site during substrate oxidation reactions.

Kink distortion of the pseudo-S4 axis in pseudotetrahedral [N2O2] bis-chelate cobalt(II) single-ion magnets leads to increased magnetic anisotropy.

Two new mononuclear cobalt(II) complexes with the general formula [Co(L1,2)2] (1 and 2) were synthesized using bidentate Schiff base ligands with NO donor set, namely, 2-(benzothiazole-2-ylimino)methyl-5-(diethylamino)phenol (HL1) and its methyl substituted derivative 2-(6-methylbenzothiazole-2-ylimino)methyl-5-(diethylamino)phenol (HL2). X-ray structure analysis reveals a distorted pseudotetrahedral coordination sphere at the cobalt(II) ion, that cannot be described by a simple twisting of the two ligand chelate planes with respect to each other, which would imply a rotation about the pseudo-S4 axis of the complex. Such a pseudo-rotation axis would approximately be colinear with the two vectors defined by the cobalt ion and the two centroids of the chelate ligands, where the angle κ between the two vectors would be 180° in an ideal pseudotetrahedral arrangement. For complexes 1 and 2, the observed distortion can be characterized by a significant bending at the cobalt ion with angles κ of 163.2° and 167.4°, respectively. Magnetic susceptibility and FD-FT THz-EPR measurements together with ab initio calculations reveal an easy-axis type of anisotropy for both complexes 1 and 2, with a spin-reversal barrier of 58.9 and 60.5 cm-1, respectively. For both compounds, frequency-dependent ac susceptibility measurements show an out-of-phase susceptibility under applied static fields of 40 and 100 mT, which can be analyzed in terms of Orbach and Raman processes within the observed temperature range.

Weakening the Interchain Interactions in One Dimensional Cobalt(II) Coordination Polymers by Preventing Intermolecular Hydrogen Bonding.

The reaction of Co(NCS)2 with N-methylaniline leads to the formation of [Co(NCS)2(N-methylaniline)2]n (1), in which the cobalt(II) cations are octahedrally coordinated and linked into linear chains by pairs of thiocyanate anions. In contrast to [Co(NCS)2(aniline)2]n (2) reported recently, in which the Co(NCS)2 chains are linked by strong interchain N-H···S hydrogen bonding, such interactions are absent in 1. Computational studies reveal that the cobalt(II) ions in compound 1 show an easy-axis anisotropy that is lower than in 2, but with the direction of the easy axis being similar in both compounds. The high magnetic anisotropy is also confirmed by magnetic and FD-FT THz-EPR spectroscopy, which yield a consistent gz value. These investigations prove that the intrachain interactions in 1 are slightly higher than in 2. Magnetic measurements reveal that the critical temperature for magnetic ordering in 1 is significantly lower than in 2, which indicates that the elimination of the hydrogen bonds leads to a weakening of the interchain interactions. This is finally proven by FD-FT THz-EPR experiments, which show that the interchain interaction energy in the N-methylaniline compound 1 is nine-fold smaller than in the aniline compound 2.

Homoleptic Fe(III) and Fe(IV) Complexes of a Dianionic C3-Symmetric Scorpionate.

High-valent iron species have been implicated as key intermediates in catalytic oxidation reactions, both in biological and synthetic systems. Many heteroleptic Fe(IV) complexes have now been prepared and characterized, especially using strongly π-donating oxo, imido, or nitrido ligands. On the other hand, homoleptic examples are scarce. Herein, we investigate the redox chemistry of iron complexes of the dianonic tris-skatylmethylphosphonium (TSMP2-) scorpionate ligand. One-electron oxidation of the tetrahedral, bis-ligated [(TSMP)2FeII]2- leads to the octahedral [(TSMP)2FeIII]-. The latter undergoes thermal spin-cross-over both in the solid state and solution, which we characterize using superconducting quantum inference device (SQUID), Evans method, and paramagnetic nuclear magnetic resonance spectroscopy. Furthermore, [(TSMP)2FeIII]- can be reversibly oxidized to the stable high-valent [(TSMP)2FeIV]0 complex. We use a variety of electrochemical, spectroscopic, and computational techniques as well as SQUID magnetometry to establish a triplet (S = 1) ground state with a metal-centered oxidation and little spin delocalization on the ligand. The complex also has a fairly isotropic g-tensor (giso = 1.97) combined with a positive zero-field splitting (ZFS) parameter D (+19.1 cm-1) and very low rhombicity, in agreement with quantum chemical calculations. This thorough spectroscopic characterization contributes to a general understanding of octahedral Fe(IV) complexes.

Experimental assignment of long-range magnetic communication through Pd & Pt metallophilic contacts.

Record-breaking magnetic exchange interactions have previously been reported for 3d-metal dimers of the form [M(Pt(SAc)4)(pyNO2)]2 (M = Ni or Co) that are linked in the solid state via metallophilic Pt⋯Pt bridges. This contrasts the terminally capped monomers [M(Pt(SAc)4)(py)2], for which neither metallophilic bridges nor magnetic exchange interactions are found. Computational modeling has shown that the magnetic exchange interaction is facilitated by the pseudo-closed shell d8⋯d8 metallophilic interaction between the filled Pt2+ 5d z 2 orbitals. We present here inelastic neutron scattering experiments on these complexes, wherein the dimers present an oscillatory momentum-transfer-dependence of the magnetic transitions. This allows for the unequivocal experimental assignment of the distance between the coupled ions, which matches exactly the coupling pathway via the metallophilic bridges. Furthermore, we have synthesized and magnetically characterized the isostructural palladium-analogues. The magnetic coupling across the Pd⋯Pd bridge is found through SQUID-magnetometry and FD-FT THz-EPR spectroscopy to be much weaker than via the Pt⋯Pt bridge. The weaker coupling is traced to the larger radial extent of the 5d z 2 orbitals compared to that of the 4d z 2 orbitals. The existence of a palladium metallophilic interaction is evaluated computationally from potential surface cuts along the metal stretching direction. Similar behavior is found for the Pd⋯Pd and Pt⋯Pt-systems with clear minima along this coordinate and provide estimates for the force constant for this distortion. The estimated M⋯M stretching frequencies are found to match experimental observed, polarized bands in single-crystal Raman spectra close to 45 cm-1. This substantiates the existence of energetically relevant Pd⋯Pd metallophilic interactions. The unique properties of both Pt2+ and Pd2+ constitutes an orthogonal reactivity, which can be utilized for steering both the direction and strength of magnetic interactions.

Spectroscopic Properties of a Biologically Relevant [Fe2 (µ-O)2 ] Diamond Core Motif with a Short Iron-Iron Distance.

Diiron cofactors in enzymes perform diverse challenging transformations. The structures of high valent intermediates (Q in methane monooxygenase and X in ribonucleotide reductase) are debated since Fe-Fe distances of 2.5-3.4 Šwere attributed to "open" or "closed" cores with bridging or terminal oxido groups. We report the crystallographic and spectroscopic characterization of a FeIII 2 (µ-O)2 complex (2) with tetrahedral (4C) centres and short Fe-Fe distance (2.52 Å), persisting in organic solutions. 2 shows a large Fe K-pre-edge intensity, which is caused by the pronounced asymmetry at the TD FeIII centres due to the short Fe-µ-O bonds. A ≈2.5 ŠFe-Fe distance is unlikely for six-coordinate sites in Q or X, but for a Fe2 (µ-O)2 core containing four-coordinate (or by possible extension five-coordinate) iron centres there may be enough flexibility to accommodate a particularly short Fe-Fe separation with intense pre-edge transition. This finding may broaden the scope of models considered for the structure of high-valent diiron intermediates formed upon O2 activation in biology.

Magnetic Anisotropy and Relaxation of Pseudotetrahedral [N2 O2 ] Bis-Chelate Cobalt(II) Single-Ion Magnets Controlled by Dihedral Twist Through Solvomorphism.

The methanol solvomorph 1 ⋅ 2MeOH of the cobalt(II) complex [Co(LSal,2-Ph )2 ] (1) with the sterically demanding Schiff-base ligand 2-(([1,1'-biphenyl]-2-ylimino)methyl)phenol (HLSal,2-Ph ) shows the thus far largest dihedral twist distortion between the two chelate planes compared to an ideal pseudotetrahedral arrangement. The cobalt(II) ion in 1 ⋅ 2MeOH exhibits an easy-axis anisotropy leading to a spin-reversal barrier of 55.3 cm-1 , which corresponds to an increase of about 17 % induced by the larger dihedral twist compared to the solvent-free complex 1. The magnetic relaxation for 1 ⋅ 2MeOH is significantly slower compared to 1. An in-depth frequency-domain Fourier-transform (FD-FT) THz-EPR study not only allowed the direct measurement of the magnetic transition between the two lowest Kramers doublets for the cobalt(II) complexes, but also revealed the presence of spin-phonon coupling. Interestingly, a similar dihedral twist correlation is also observed for a second pair of cobalt(II)-based solvomorphs, which could be benchmarked by FD-FT THz-EPR.

A New Thiolate-Bound Dimanganese Cluster as a Structural and Functional Model for Class Ib Ribonucleotide Reductases.

In class Ib ribonucleotide reductases (RNRs) a dimanganese(II) cluster activates superoxide (O2 ⋅- ) rather than dioxygen (O2 ), to access a high valent MnIII -O2 -MnIV species, responsible for the oxidation of tyrosine to tyrosyl radical. In a biomimetic approach, we report the synthesis of a thiolate-bound dimanganese complex [MnII 2 (BPMT)(OAc)2 ](ClO)4 (BPMT=(2,6-bis{[bis(2-pyridylmethyl)amino]methyl}-4-methylthiophenolate) (1) and its reaction with O2 ⋅- to form a [(BPMT)MnO2 Mn]2+ complex 2. Resonance Raman investigation revealed the presence of an O-O bond in 2, while EPR analysis displayed a 16-line St =1/2 signal at g=2 typically associated with a MnIII MnIV core, as detected in class Ib RNRs. Unlike all other previously reported Mn-O2 -Mn complexes, generated by O2 ⋅- activation at Mn2 centers, 2 proved to be a capable electrophilic oxidant in aldehyde deformylation and phenol oxidation reactions, rendering it one of the best structural and functional models for class Ib RNRs.

Evidence of Sulfur Non-Innocence in [CoII (dithiacyclam)]2+ -Mediated Catalytic Oxygen Reduction Reactions.

In many metalloenzymes, sulfur-containing ligands participate in catalytic processes, mainly via the involvement in electron transfer reactions. In a biomimetic approach, we now demonstrate the implication of S-ligation in cobalt mediated oxygen reduction reactions (ORR). A comparative study between the catalytic ORR capabilities of the four-nitrogen bound [Co(cyclam)]2+ (1; cyclam=1,5,8,11-tetraaza-cyclotetradecane) and the S-containing analog [Co(S2 N2 -cyclam)]2+ (2; S2 N2 -cyclam=1,8-dithia-5,11-diaza-cyclotetradecane) reveals improved catalytic performance once the chalcogen is introduced in the Co coordination sphere. Trapping and characterization of the intermediates formed upon dioxygen activation at the CoII centers in 1 and 2 point to the involvement of sulfur in the O2 reduction process as the key for the improved catalytic ORR capabilities of 2.

Antisymmetric Spin Exchange in a µ-1,2-Peroxodicopper(II) Complex with an Orthogonal Cu-O-O-Cu Arrangement and S = 1 Spin Ground State Characterized by THz-EPR.

A unique type of Cu2/O2 adduct with orthogonal (close to 90°) Cu-O-O-Cu arrangement has been proposed for initial stages of O2 binding at biological type III dicopper sites, and targeted ligand design has now allowed us to emulate such an adduct in a pyrazolate-based µ-η1 :η1-peroxodicopper(II) complex (2) with Cu-O-O-Cu torsion φ of 87°, coined ⊥ P intermediate. Full characterization of 2, including X-ray diffraction (d O-O = 1.452 Å) and Raman spectroscopy (ν̃O-O = 807 cm-1), completes a series of closely related Cu2/O2 intermediates featuring µ-η1 :η1-peroxodicopper(II) cores with φ ranging from 55° (A, cis-peroxo C P; Brinkmeier A.et al., J. Am. Chem. Soc.2021, 143, 10361) via 87° (2, ⊥ P type) up to 104° (B, approaching trans-peroxo T P; Kindermann N.et al., Angew. Chem., Int. Ed.2015, 54, 1738). SQUID magnetometry revealed ferromagnetic interaction of the CuII ions and a triplet (S t = 1) ground state in 2. Frequency-domain THz-EPR has been employed to quantitatively investigate the spin systems of 2 and B. Magnetic transitions within the triplet ground states confirmed their substantial zero-field splittings (ZFS) suggested by magnetometry. Formally forbidden triplet-to-singlet transitions at 56 (2) and 157 cm-1 (B), which are in agreement with the exchange coupling strengths J iso inferred from SQUID data, are reported for the first time for coupled dicopper(II) complexes. Rigorous analysis by spin-Hamiltonian-based simulations attributed the corresponding nonzero transition probabilities and the ZFS to substantial antisymmetric (Dzyaloshinskii-Moriya) exchange d and provided robust values and orientations for the d , J , and g tensors. These interactions can be correlated with the Cu-O-O-Cu geometries, revealing a linear increase of J iso with the Cu-O-O-Cu torsion and a strong linear decrease with the Cu-O-O angle. Relevance of the ⊥ P intermediate for O2 activation at type III dicopper sites and a potential role of antisymmetric exchange in the concomitant intersystem crossing are proposed.

Sequential Hydrogen Tunneling in o-Tolylmethylene.

o-Tolylmethylene 1 is a metastable triplet carbene that rearranges to o-xylylene 2 even at temperatures as low as 2.7 K via [1,4] H atom tunneling. Electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopical techniques were used to identify two conformers of 1 (anti and syn) in noble gas matrices and in frozen organic solutions. Conformer-specific kinetic measurements revealed that the rate constants for the rearrangements of the anti and syn conformers of 1 are very similar. However, the orbital alignment in the syn conformer is less favorable for the hydrogen transfer reaction than the orbital configuration in the anti conformer. Our spectroscopic and quantum chemical investigations indicate that anti 1 and syn 1 rapidly interconvert via efficient quantum tunneling forming a rotational pre-equilibrium. The subsequent second tunneling reaction, the [1,4] H migration from anti 1 to 2, is rate-limiting for the formation of 2. We here present an efficient strategy for the study of such tunneling equilibria.

Single-Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High Spin and 5/2-3/2 Spin Admixture.

A mononuclear iron(III) porphyrin compound exhibiting unexpectedly slow magnetic relaxation, which is a characteristic of single-ion magnet behaviour, is reported. This behaviour originates from the close proximity (≈550 cm-1 ) of the intermediate-spin S=3/2 excited states to the high-spin S=5/2 ground state. More quantitatively, although the ground state is mostly S=5/2, a spin-admixture model evidences a sizable contribution (≈15 %) of S=3/2 to the ground state, which as a consequence experiences large and positive axial anisotropy (D=+19.2 cm-1 ). Frequency-domain EPR spectroscopy allowed the mS = |±1/2⟩→|±3/2⟩ transitions to be directly accessed, and thus the very large zero-field splitting in this 3d5 system to be unambiguously measured. Other experimental results including magnetisation, Mössbauer, and field-domain EPR studies are consistent with this model, which is also supported by theoretical calculations.

Influence of the Coligand onto the Magnetic Anisotropy and the Magnetic Behavior of One-Dimensional Coordination Polymers.

Reaction of Co(NCS)2 with different coligands leads to the formation of three compounds with the general composition [Co(NCS)2(L)2]n (L = aniline (1), morpholine (2), and ethylenethiourea (3)). In all of these compounds the cobalt(II) cations are octahedrally coordinated by two trans thiocyanate N and S atoms and the apical donor atoms of the coligands and are linked into linear chains by pairs of anionic ligands. The magnetic behavior was investigated by a combination of static and dynamic susceptibility as well as specific-heat measurements, computational studies, and THz-EPR spectroscopy. All compounds show antiferromagnetic ordering as observed for similar compounds with pyridine derivatives as coligands. In contrast to the latter, for 1-3 significantly higher critical temperatures and no magnetic single-chain relaxations are observed, which can be traced back to stronger interchain interactions and a drastic change in the magnetic anisotropy of the metal centers. These results are discussed and compared with those of the pyridine-based compounds, which provides important insights into the parameters that govern the magnetic behavior of such one-dimensional coordination polymers.

Variation of the Chain Geometry in Isomeric 1D Co(NCS)2 Coordination Polymers and Their Influence on the Magnetic Properties.

Two different isomers of [Co(NCS)2(4-chloropyridine)2]n (3C and 3L) were synthesized from solution and by thermal decomposition of Co(NCS)2(4-chloropyridine)2(H2O)2 (2), which show a different metal coordination leading to corrugated chains in 3C and to linear chains in 3L. Solvent mediated conversion experiments prove that 3C is thermodynamically stable at room temperature where 3L is metastable. Magnetic measurements reveal that the magnetic exchange in 3L is comparable to that observed for previously reported related chain compounds, whereas in 3C with corrugated chains, the ferromagnetic interaction within the chains is strongly suppressed. The magnetic ordering takes place at 2.85 and 0.89 K, for 3L and 3C, respectively, based on specific heat measurements. For 3L the field dependence of magnetic relaxations in antiferromagnetically ordered ferromagnetic chains is presented. In addition, 3L is investigated by FD-FT THz-EPR spectroscopy, revealing a ground to first excited state energy gap of 14.0 cm-1. Broken-symmetry DFT calculations for 3C and 3L indicate a ferromagnetic intrachain interaction. Ab initio CASSCF/CASPT2/RASSI-SO computational studies reveal significantly different single-ion anisotropies for the crystallographically independent cobalt(II) centers in 3C and 3L. Together with the geometry of the chains this explains the magnetic properties of 3C and 3L. The ab initio results also explain the weaker exchange interaction in 3C and 3L as compared to previously reported [Co(NCS)2(L)2]n compounds with linear chains.

Single-Chain Magnet Based on Cobalt(II) Thiocyanate as XXZ Spin Chain.

Invited for the cover of this issue is the group of Michal Rams at Jagiellonian University (Kraków, Poland) and colleagues at Christian-Albrechts-Universität zu Kiel, Friedrich-Schiller-Universität Jena, and Helmholtz-Zentrum Berlin. The image represents a 1D coordination polymer with Co(II) spins that are flipped by photons during an EPR experiment. Read the full text of the article at 10.1002/chem.201903924.

Single-Chain Magnet Based on Cobalt(II) Thiocyanate as XXZ Spin Chain.

The cobalt(II) in [Co(NCS)2 (4-methoxypyridine)2 ]n are linked by pairs of thiocyanate anions into linear chains. In contrast to a previous structure determination, two crystallographically independent cobalt(II) centers have been found to be present. In the antiferromagnetic state, below the critical temperature (Tc =3.94 K) and critical field (Hc =290 Oe), slow relaxations of the ferromagnetic chains are observed. They originate mainly from defects in the magnetic structure, which has been elucidated by micromagnetic Monte Carlo simulations and ac measurements using pristine and defect samples. The energy barriers of the relaxations are Δτ1 =44.9(5) K and Δτ2 =26.0(7) K for long and short spin chains, respectively. The spin excitation energy, measured by using frequency-domain EPR spectroscopy, is 19.1 cm-1 and shifts 0.1 cm-1 due to the magnetic ordering. Ab initio calculations revealed easy-axis anisotropy for both CoII centers, and also an exchange anisotropy Jxx /Jzz of 0.21. The XXZ anisotropic Heisenberg model (solved by using the density renormalization matrix group technique) was used to reconcile the specific heat, susceptibility, and EPR data.

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.

Light-controlled switching of the spin state of iron(III).

Controlled switching of the spin state of transition metal ions, particularly of FeII and FeIII, is a prerequisite to achieve selectivity, efficiency, and catalysis in a number of metalloenzymes. Here we report on an iron(III) porphyrin with a photochromic axial ligand which, upon irradiation with two different wavelengths reversibly switches its spin state between low-spin (S = 1/2) and high-spin (S = 5/2) in solution (DMSO-acetone, 2:598). The switching efficiency is 76% at room temperature. The system is neither oxygen nor water sensitive, and no fatigue was observed after more than 1000 switching cycles. Concomitant with the spin-flip is a change in redox potential by ~60 mV. Besides serving as a simple model for the first step of the cytochrome P450 catalytic cycle, the spin switch can be used to switch the spin-lattice relaxation time T1 of the water protons by a factor of 15.

Reactions of Cyclopentadienylidenes with CF3I: Electron Bond Donation versus Halogen Bond Donation of the Iodine Atom.

The interaction of cyclopentadienylidene and tetrachlorocyclopentadienylidene with the halogen bond donor CF3I has been studied by matrix isolation spectroscopy. The carbenes were produced by photolysis of the corresponding diazo compounds, matrix-isolated in argon doped with 1% CF3I at 3 K. Bimolecular reactions between the carbenes and CF3I were induced by annealing these matrices to 25-30 K to allow for the diffusion of trapped species. Instead of classical halogen-bonded complexes, these carbenes form complexes in which the iodine atom is shared between the carbene center and the CF3 group. Photolysis of the complexes at 3 K yields radical pairs, which reversibly react back to the complexes when the matrices are warmed to 25-30 K.