Diversity of oxidation state in copper complexes with phenolate ligands.

The phenoxyl radical binding copper complexes have been widely developed and their detailed geometric and electronic structures have been clarified. While many one-electron oxidized CuII-phenolate complexes have been reported previously, recent studies of the Cu-phenolate complexes proceed toward elucidation of the complexes with other oxidation states, such as the phenoxyl radical binding CuI complexes and CuIV-phenolate complexes in the formal oxidation state. This Perspective focuses on new aspects of the properties and reactivities of various Cu-phenolate and Cu-phenoxyl radical complexes with emphasis on the relationship between geometric and electronic structures.

Syntheses, Characterizations, Crystal Structures, and Protonation Reactions of Dinitrogen Chromium Complexes Supported with Triamidoamine Ligands.

A novel dinitrogen-dichromium complex, [{Cr(LBn)}2(µ-N2)] (1), has been prepared from reaction of CrCl3 with a lithiated triamidoamine ligand (Li3LBn) under dinitrogen. The X-ray crystal structure analysis of 1 revealed that it is composed of two independent dimeric Cr complexes bridged by N2 in the unit cell. The bridged N-N bond lengths (1.188(4) and 1.185(7) Å) were longer than the free dinitrogen molecule. The elongations of N-N bonds in 1 were also supported by the fact that the ν(N-N) stretching vibration at 1772 cm-1 observed in toluene is smaller than the free N2. Complex 1 was identified to be a 5-coordinated high spin Cr(IV) complex by Cr K-edge XANES measurement. The 1H NMR spectrum and temperature dependent magnetic susceptibility of 1 indicated that complex 1 is in the S = 1 ground state, in which two Cr(IV) ions and unpaired electron spins of the bridging N22- ligand are strongly antiferromagnetically coupled. Reaction of complex 1 with 2.3 equiv of Na or K gave chromium complexes with N2 between the Cr ion and the respective alkali metal ion, [{CrNa(LBn)(N2)(Et2O)}2] (2) and [{CrK(LBn)(N2)}4(Et2O)2] (3), respectively. Furthermore, the complexes 2 and 3 reacted with 15-crown-5 and 18-crown-6 to form the respective crown-ether adducts, [CrNa(LBn)(N2)(15-crown-5)] (4) and [CrK(LBn)(N2)(18-crown-6)] (5). The XANES measurements of complexes 2, 3, 4, and 5 revealed that they are high spin Cr(IV) complexes like complex 1. All complexes reacted with a reducing agent and a proton source to form NH3 and/or N2H4. The yields of these products in the presence of K+ were higher than those in the presence of Na+. The electronic structures and binding properties of 1, 2, 3, 4, and 5 were evaluated and discussed based on their DFT calculations.

Non-innocent redox behavior of CuII-p-dimethylaminophenolate complexes: formation and characterization of the CuI-phenoxyl radical species.

Cu complexes with p-dimethylaminophenolate ligands were synthesized by the reaction of CuII ions with the ligands under inert gas atmosphere and characterized. The complexes showed a valence state change from CuII-phenolate to CuI-phenoxyl radical on loss of the coordinated solvent. The CuI-phenoxyl radical species showed the characteristic properties and reactivities.

π-π Stacking Interaction of Metal Phenoxyl Radical Complexes.

π-π stacking interaction is well-known to be one of the weak interactions. Its importance in the stabilization of protein structures and functionalization has been reported for various systems. We have focused on a single copper oxidase, galactose oxidase, which has the π-π stacking interaction of the alkylthio-substituted phenoxyl radical with the indole ring of the proximal tryptophan residue and catalyzes primary alcohol oxidation to give the corresponding aldehyde. This stacking interaction has been considered to stabilize the alkylthio-phenoxyl radical, but further details of the interaction are still unclear. In this review, we discuss the effect of the π-π stacking interaction of the alkylthio-substituted phenoxyl radical with an indole ring.

Formation of Ni(II)-phenoxyl radical complexes by O2: a mechanistic insight into the reaction of Ni(II)-phenol complexes with O2.

A reaction of Ni(ClO4)2·6H2O with a tripodal ligand having two di(tert-butyl)phenol moieties, H2tbuL, and 1 equivalent of triethylamine in CH2Cl2/CH3OH (1 : 1, v/v) under N2 gave a NiII-(phenol)(phenolate) complex, [Ni(HtbuL)(CH3OH)2]ClO4. The formation of the NiII-phenoxyl radical complex by O2 was observed in the reaction of this complex in the solid state. On the other hand, the NiII-phenoxyl radical complex [Ni(Me2NL)(CH3OH)2]ClO4 was obtained by the reaction of H2Me2NL having a p-(dimethylamino)phenol moiety with Ni(ClO4)2·6H2O in a similar procedure under O2, through the oxidation of the NiII-(phenol)(phenolate) complex. However, a direct redox reaction of the NiII ion could not be detected in the phenoxyl radical formation. The results of the reaction kinetics, XAS and X-ray structure analyses suggested that the O2 oxidation from the NiII-(phenol)(phenolate) complex to the NiII-phenoxyl radical complex occurs via the proton transfer-electron transfer (PT-ET) type mechanism of the phenol moiety weakly coordinated to the nickel ion.

Recent Advances in One-Electron-Oxidized CuII -Diphenoxide Complexes as Models of Galactose Oxidase: Importance of the Structural Flexibility in the Active Site.

The phenoxyl radical plays important roles in biological systems as cofactors in some metalloenzymes, such as galactose oxidase (GO) catalyzing oxidation of primary alcohols to give the corresponding aldehydes. Many metal(II)-phenoxyl radical complexes have hitherto been studied for understanding the detailed properties and reactivities of GO, and thus the nature of GO has gradually become clearer. However, the effects of the subtle geometric and electronic structural changes at the active site of GO, especially the structural change in the catalytic cycle and the effect of the second coordination sphere, have not been fully discussed yet. In this Review, we focus on further details of the model studies of GO and discuss the importance of the structural change at the active site of GO.

Formation of the CuII -Phenoxyl Radical by Reaction of O2 with a CuII -Phenolate Complex via the CuI -Phenoxyl Radical.

Reaction of Cu(ClO4 )2 ⋅6 H2 O with a tripodal 2N2O ligand, H2 Me2 NL, having a p-(dimethylamino)phenol moiety, in CH2 Cl2 /MeOH (1:1 v/v) under basic conditions under an inert gas atmosphere gave [Cu(Me2 NL)(H2 O)] (1). The same reaction carried out under aerobic conditions gave [Cu(Me2 NL)(MeOH)]ClO4 (2), which could be obtained also from the isolated complex 1 by reaction with O2 in CH2 Cl2 /MeOH. The X-ray crystal structures of 1 and 2 revealed similar square-pyramidal structures, but 2 showed the (dimethylamino)phenoxyl radical features. Complex 1 exhibits characteristic CuII EPR signals of the d x 2 - y 2 ground state in CH2 Cl2 /MeOH at 77 K, whereas 2 is EPR-silent. The EPR and X-ray absorption fine structure (XAFS) results suggest that 2 is assigned to the CuII -(dimethylamino)phenoxyl radical. However, complex 1 showed different features in the absence of MeOH. The EPR spectrum of the CH2 Cl2 solution of 1 exhibits distortion from the d x 2 - y 2 ground state and a temperature-dependent equilibrium between the CuII -(dimethylamino)phenolate and the CuI -(dimethylamino)phenoxyl radical. From these results, CuII -phenoxyl radical complex 2 is concluded to be formed by the reaction of 1 with O2 via the CuI -phenoxyl radical species.

The effect of π-π stacking interaction of the indole ring with the coordinated phenoxyl radical in a nickel(ii)-salen type complex. Comparison with the corresponding Cu(ii) complex.

In order to gain new insights into the effect of the π-π stacking interaction of the indole ring with the phenoxyl radical moiety as seen in the active form of galactose oxidase, we have prepared Ni(ii) complexes of a methoxy substituted salen-type ligand containing a pendent indole ring on the dinitrogen chelate backbone and characterized their one-electron oxidized forms. The X-ray crystal structure analysis and the other physicochemical experiments of the Ni(ii) complex revealed no significant intramolecular interaction of the indole ring with the coordination plane. On the other hand, the X-ray crystal structures of the oxidized Ni(ii) complex exhibited the π-π stacking interaction of the indole ring mainly with one of the two phenolate moieties. While the phenoxyl radical electron was delocalized on the two phenolate moieties in the Ni(ii)-salen coordination plane, the phenolate moiety in close contact with the indole moiety was considered to be the initial oxidation locus, indicating that the indole ring interacted with the phenoxyl radical by π-π stacking. The UV-vis-NIR spectrum of the oxidized Ni(ii) complex with the pendent indole ring was different from that of the complex without the side chain indole ring, but the differences were rather small in comparison with the oxidized Cu(ii)-salen complexes with the π-π stacking interaction of the indole ring. Such differences are due to the electronic structure difference, the localized radical electron on one of the phenolate moieties in the oxidized Cu(ii) complexes being more favorable for the π-π stacking interaction.

π-π Stacking Interaction in an Oxidized CuII -Salen Complex with a Side-Chain Indole Ring: An Approach to the Function of the Tryptophan in the Active Site of Galactose Oxidase.

In order to gain new insights into the effect of the π-π stacking interaction of the indole ring with the CuII -phenoxyl radical as seen in the active form of galactose oxidase, we have prepared a CuII complex of a methoxy-substituted salen-type ligand, containing a pendent indole ring on the dinitrogen chelate backbone, and characterized its one-electron-oxidized forms. The X-ray crystal structures of the oxidized CuII complex exhibited the π-π stacking interaction of the indole ring mainly with one of the two phenolate moieties. The phenolate moiety in close contact with the indole moiety showed the characteristic phenoxyl radical structural features, indicating that the indole ring favors the π-π stacking interaction with the phenoxyl radical. The UV/Vis/NIR spectra of the oxidized CuII complex with the pendent indole ring was significantly different from those of the complex without the side-chain indole ring, and the absorption and CD spectra exhibited a solvent dependence, which is in line with the phenoxyl radical-indole stacking interaction in solution. The other physicochemical results and theoretical calculations strongly support that the indole ring, as an electron donor, stabilizes the phenoxyl radical by the π-π stacking interaction.

Electronic Structure and Reactivity Studies of a Nonsymmetric One-Electron Oxidized CuII Bis-phenoxide Complex.

The tetradentate mixed imino/amino phenoxide ligand (N-(3,5-di-tert-butylsalicylidene)-N'-(2-hydroxyl-3,5-di-tert-butylbenzyl))-trans-1,2-cyclohexanediamine (salalen) was complexed with CuII, and the resulting Cu complex (2) was characterized by a number of experimental techniques and theoretical calculations. Two quasi-reversible redox processes for 2, as observed by cyclic voltammetry, demonstrated the potential stability of oxidized forms, and also the increased electron-donating ability of the salalen ligand in comparison to the salen analogue. The electronic structure of the one-electron oxidized [2]+ was then studied in detail, and Cu K-edge X-ray Absorption Spectroscopy (XAS) measurements confirmed a CuII-phenoxyl radical complex in solution. Subsequent resonance Raman (rR) and variable temperature 1H NMR studies, coupled with theoretical calculations, showed that [2• ]+ is a triplet (S = 1) CuII-phenoxyl radical species, with localization of the radical on the more electron-rich aminophenoxide. Attempted isolation of X-ray quality crystals of [2• ]+ afforded [2H]+, with a protonated phenol bonded to CuII, and an additional H-bonding interaction with the SbF6 - counterion. Stoichiometric reaction of dilute solutions of [2• ]+ with benzyl alcohol showed that the complex reacted in a similar manner as the oxidized CuII-salen analogue, and does not exhibit a substrate-binding pre-equilibrium as observed for the oxidized bisaminophenoxide CuII-salan derivative.

Characterization of the one-electron oxidized Cu(II)-salen complexes with a side chain aromatic ring: the effect of the indole ring on the Cu(II)-phenoxyl radical species.

To gain insights into the role of the proximal indole ring in the redox-active metal center as seen in galactose oxidase, we prepared the Cu(II)-salen-type complexes having a pendent indol-3-ylmethyl (1), methyl (2) or benzyl (3) group substituted on the ethylenediamine moiety and investigated the structures and redox properties by various physicochemical methods and theoretical calculations. Neutral complexes 1, 2, and 3 showed no significant difference in the UV-Vis-NIR and EPR spectra. One-electron oxidation of 1, 2, and 3 by addition of 1 equiv. of thianthrenyl radical gave [1]SbCl 6 , [2]SbCl 6 , and [3]SbCl 6 , respectively, which could be assigned to relatively localized phenoxyl radical species. The cyclic and differential pulse voltammograms of [1]SbCl 6 showed two redox waves with a large separation between the first and second redox potentials compared with the separations observed for [2]SbCl 6 and [3]SbCl 6 . This suggests that [1]SbCl 6 is more stabilized than [2]SbCl 6 and [3]SbCl 6 . The NIR band of [1]SbCl 6 showed a larger blue shift than that of [2]SbCl 6 and [3]SbCl 6 . The EPR spectrum of [2]SbCl 6 exhibited an intense signal at the g value of 2 due to partial disproportionation to form the EPR active two-electron oxidized complex [2] 2+ , while the EPR intensity of [1]SbCl 6 was much weaker than that of [2]SbCl 6 . These results indicate that the pendent indole moiety stabilizes the Cu(II)-phenoxyl radical in [1]SbCl 6 most probably by stacking with the phenoxyl moiety, which is further supported by DFT calculations.

Properties of the indole ring in metal complexes. A comparison with the phenol ring.

Tryptophan (Trp), an essential amino acid, has an indole ring with a high electron density and is frequently seen at the proximal position of the metal site in metalloproteins. For example, the indole ring of Trp has been reported to interact weakly with Cu(I) in a Cu chaperone CusF. Another aromatic amino acid, tyrosine (Tyr), has a phenol ring, which is an important metal binding site in various metalloproteins. Although the structures of the aromatic rings are different, they both have a weakly acidic moiety and perform some similar roles in biological systems, such as radical formation and electron transfer. In this review, we focus on these and other properties of the indole and phenol rings in metal-containing systems.

Influence of ligand flexibility on the electronic structure of oxidized Ni(III)-phenoxide complexes.

One-electron-oxidized Ni(III)-phenoxide complexes with salen-type ligands, [Ni(salen)py2](2+) ([1(en)-py](2+)) and [Ni(1,2-salcn)py2](2+) ([1(cn)-py](2+)), with a five-membered chelate dinitrogen backbone and [Ni(salpn)py2](2+) ([2(pn)-py](2+)), with a six-membered chelate backbone, have been characterized with a combination of experimental and theoretical methods. The five-membered chelate complexes [1(en)-py](2+) and [1(cn)-py](2+) were assigned as Ni(III)-phenoxyl radical species, while the six-membered chelate complex [2(pn)-py](2+) was concluded to be a Ni(II)-bis(phenoxyl radical) species with metal-centered reduction in the course of the one-electron oxidation of the Ni(III)-phenoxide complex [2(pn)-py](+). Thus, the oxidation state of the one-electron-oxidized Ni(III) salen-type complexes depends on the chelate ring size of the dinitrogen backbone.

Fe(III) bipyrrolidine phenoxide complexes and their oxidized analogues.

Fe(III) complexes of the symmetric (2S,2'S)-[N,N'-bis(1-(2-hydroxy-3,5-di-tert-butylphenylmethyl))]-2,2'-bipyrrolidine (H2L(1)) and dissymmetric (2S,2'S)-[N,N'-(1-(2-hydroxy-3,5-di-tert-butylphenylmethyl))-2-(pyridylmethyl)]-2,2'-bipyrrolidine (HL(2)) ligands incorporating the bipyrrolidine backbone were prepared, and the electronic structure of the neutral and one-electron oxidized species was investigated. Cyclic voltammograms (CV) of FeL(1)Cl and FeL(2)Cl2 showed expected redox waves corresponding to the oxidation of phenoxide moieties to phenoxyl radicals, which was achieved by treating the complexes with 1 equiv of a suitable chemical oxidant. The clean conversion of the neutral complexes to their oxidized forms was monitored by UV-vis-NIR spectroscopy, where an intense π-π* transition characteristic of a phenoxyl radical emerged ([FeL(1)Cl](+•): 25,500 cm(-1) (9000 M(-1) cm(-1)); [FeL(2)Cl2](+•): 24,100 cm(-1) (8300 M(-1) cm(-1)). The resonance Raman (rR) spectra of [FeL(1)Cl](+•) and [FeL(2)Cl2](+•) displayed the characteristic phenoxyl radical ν7a band at 1501 and 1504 cm(-1), respectively, confirming ligand-based oxidation. Electron paramagnetic resonance (EPR) spectroscopy exhibited a typical high spin Fe(III) (S = 5/2) signal for the neutral complexes in perpendicular mode. Upon oxidation, a signal at g ≈ 9 was observed in parallel mode, suggesting the formation of a spin integer system arising from magnetic interactions between the high spin Fe(III) center and the phenoxyl radical. Density functional theory (DFT) calculations further supports this formulation, where weak antiferromagnetic coupling was predicted for both [FeL(1)Cl](+•) and [FeL(2)Cl2](+•).

Characterization of one-electron oxidized copper(II)-salophen-type complexes; effects of electronic and geometrical structures on reactivities.

One-electron oxidized salophen-type complexes, [Cu(salophen)](+) (H2salophen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminobenzene), and its methoxy derivatives, [Cu(MeO-salophen)](+) and [Cu(salophen-(MeO)2)](+) (H2MeO-salophen = N,N'-bis(3-tert-butyl-5-methoxysalicylidene)-1,2-diaminobenzene, H2salophen-(MeO)2 = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-diamino-4,5-dimethoxybenzene), have been synthesized and structurally characterized, and their reactivities have been investigated. The solid state structures of the one-electron oxidized forms of these complexes suggested that [Cu(salophen)](+) and [Cu(MeO-salophen)](+) can be assigned to relatively localized Cu(ii)-phenoxyl radical complexes, while [Cu(salophen-(MeO)2)](+) is the diiminobenzene radical complex. On the other hand, [Cu(salophen)](+) in solution showed a different electronic structure from that of the solid sample, the radical electron being delocalized over the whole π-conjugated ligand. The reaction of these oxidized complexes with benzyl alcohol has been investigated in the presence of a large excess of substrate, which revealed the difference in the kinetic behavior between the complexes. The mechanisms of the oxidation have been discussed on the basis of the electronic and geometrical structures and the reaction kinetics.

Double oxidation localizes spin in a Ni bis-phenoxyl radical complex.

The electronic structure of a doubly oxidized Ni salen complex NiSal(tBu) (Sal(tBu) = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) has been investigated by both experimental and theoretical methods. The doubly oxidized product was probed by resonance Raman spectroscopy, UV-vis-NIR, and EPR to determine the locus of oxidation as well as the spectroscopic signature of the complex. It was determined that double oxidation of NiSal(tBu) affords a bis-ligand radical species in solution via the presence of phenoxyl radical bands at ν(7a) (1504 cm(-1)) and ν(8a) (1579 cm(-1)) in the Raman spectrum, and the loss of the intense NIR transition reported for the mono-radical complex (Angew. Chem., Int. Ed., 2007, 46, 5198). Spectroscopic experiments, complemented by DFT calculations, show that the two radical spins are predominantly localized on the phenolate moieties, in opposition to the extensive delocalization over the ligand framework observed for the mono-radical analogue.

New insights into the electronic structure and reactivity of one-electron oxidized copper(II)-(disalicylidene)diamine complexes.

The neutral and one-electron oxidized Cu(II) six-membered chelate 1,3-Salcn (1,3-Salcn = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,3-cyclohexanediamine) complexes have been investigated and compared with the five-membered chelate 1,2-Salcn (N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) complexes. Cyclic voltammetry of Cu(1,3-Salcn) showed two reversible redox waves at 0.48 and 0.68 V, which are only 0.03 V higher than those of Cu(1,2-Salcn). Reaction of Cu(1,3-Salcn) with 1 equiv of AgSbF6 afforded the oxidized complex which exists as a ligand-based radical species in solution and in the solid state. The X-ray crystal structure of the oxidized complex, [Cu(1,3-Salcn)]SbF6, exhibited an asymmetric metal binding environment with a longer Cu-O bond and quinoid distortion in the phenolate moiety on one side, demonstrating at least partial ligand radical localization in the solid state. The ligand oxidation is also supported by XPS and temperature dependent magnetic susceptibility. The electronic structure of the [Cu(1,3-Salcn)](+) complex was further probed by UV-vis-NIR, resonance Raman, and electron paramagnetic resonance (EPR) measurements, and by theoretical calculations, indicating that the phenoxyl radical electron is relatively localized on one phenolate moiety in the molecule. The reactivity of [Cu(1,3-Salcn)](+) with benzyl alcohol was also studied. Quantitative conversion of benzyl alcohol to benzaldehyde was observed, with a faster reaction rate in comparison with [Cu(1,2-Salcn)](+). The kinetic isotope effect (KIE = k(H)/k(D)) of benzyl alcohol oxidation by [Cu(1,3-Salcn)](+) was estimated to be 13, which is smaller than the value reported for [Cu(1,2-Salcn)](+). The activation energy difference between [Cu(1,2-Salcn)](+) and [Cu(1,3-Salcn)](+) was in good agreement with the energy calculated from KIE. This correlation suggests that the Cu(II)-phenoxyl radical species, characterized for [Cu(1,2-salcn)](+) is more reactive for hydrogen abstraction from benzyl alcohol in comparison to the 1:1 mixture of Cu(III)-phenolate and Cu(II)-phenoxyl radical species, [Cu(1,2-Salcn)](+). Thus, the Cu(II)-phenoxyl radical species accelerates benzyl alcohol oxidation in comparison with the Cu(III)-phenolate ground state complex, in spite of the similar activated intermediate and oxidation pathway.

Group-10 metal complexes of biological molecules and related ligands: structural and functional properties.

The complexes of group-10 metals, Ni, Pd, and Pt, with biological molecules and related ligands have been attracting increasing attention in recent years due to their reactivities and functions, such as catalysts and drugs, and their biological relevance. The well-defined structures and kinetic inertness especially of Pt complexes have been used as the sites for weak interactions with other molecules. The Ni complexes have been reported as models not only for Ni enzymes but also for other metalloenzyme active sites for deeper understanding of the reactivities such as oxygen activations and detailed electronic structures. Pd Complexes are widely known for their catalytic activities in conversions of various organic molecules including useful biological molecules, such as Suzuki-Miyaura cross-coupling, while Pt complexes have been intensively studied for their antitumor activities. We focus in this review on our recent results on weak interactions and reactivities of the group-10 metal complexes with biological molecules and related compounds, and discuss their structural features and some new properties pointing to functional possibilities.

Radical localization in a series of symmetric Ni(II) complexes with oxidized salen ligands.

Square-planar nickel(II) complexes of salen ligands, N,N'-bis(3-tert-butyl-(5R)-salicylidene)-1,2-cyclohexanediamine), in which R=tert-butyl (1), OMe (2), and NMe(2) (3), were prepared and the electronic structure of the one-electron-oxidized species [1-3](+·) was investigated in solution. Cyclic voltammograms of [1-3] showed two quasi-reversible redox waves that were assigned to the oxidation of the phenolate moieties to phenoxyl radicals. From the difference between the first and second redox potentials, the trend of electronic delocalization 1(+·) >2(+·) >3(+·) was obtained. The cations [1-3](+·) exhibited isotropic g tensors of 2.045, 2.023, and 2.005, respectively, reflecting a lower metal character of the singly occupied molecular orbital (SOMO) for systems that involve strongly electron-donating substituents. Pulsed-EPR spectroscopy showed a single population of equivalent imino nitrogen atoms for 1(+·), whereas two distinct populations were observed for 2(+·). The resonance Raman spectra of 2(+·) and 3(+·) displayed the ν(8a) band of the phenoxyl radicals at 1612 cm(-1), as well as the ν(8a) bands of the phenolates. In contrast, the Raman spectrum of 1(+·) exhibited the ν(8a) band at 1602 cm(-1), without any evidence of the phenolate peak. Previous work showed an intense near-infrared (NIR) electronic transition for 1(+·) (Δν(1/2) =660 cm(-1), ε=21,700 M(-1) cm(-1)), indicating that the electron hole is fully delocalized over the ligand. The broader and moderately intense NIR transition of 2(+·) (Δν(1/2) =1250 cm(-1) , ε=12,800 M(-1) cm(-1)) suggests a certain degree of ligand-radical localization, whereas the very broad NIR transition of 3(+·) (Δν(1/2) =8630 cm(-1), ε=2550 M(-1) cm(-1)) indicates significant localization of the ligand radical on a single ring. Therefore, 1(+·) is a Class III mixed-valence complex, 2(+·) is Class II/III borderline complex, and 3(+·) is a Class II complex according to the Robin-Day classification method. By employing the Coulomb-attenuated method (CAM-B3LYP) we were able to predict the electron-hole localization and NIR transitions in the series, and show that the energy match between the redox-active ligand and the metal d orbitals is crucial for delocalization of the radical SOMO.

Non-innocent ligand behaviour of a bimetallic Cu complex employing a bridging catecholate.

The geometric and electronic structure of a bimetallic Cu Schiff-base complex and its one-electron oxidized form have been investigated. The two salen units in the neutral complex 1 are linked via a bridging catecholate function, and the coupling between the two Cu(II) d(9) centres was determined to be weakly antiferromagnetic on the basis of solid-state magnetic studies (J = -3 cm(-1)), and variable-temperature electron paramagnetic resonance (EPR) (J = -3 cm(-1)). Theoretical calculations (DFT) were in agreement with the experimental results (J = -7 cm(-1)), and provided insight into the coupling mechanism for the neutral system. One-electron oxidation provided [1](+) which was observed to have limited stability in solution. The oxidized complex was determined to be a ligand radical species in solution, with the electron hole potentially localized on the redox-active dioxolene, the phenolate ligands, or delocalized over the entire ligand system. Electrochemical experiments and UV-vis-NIR spectroscopy, in combination with density functional theory (DFT) calculations, provided insight into the locus of oxidation and the degree of delocalization in this system. The ligand radical for [1˙](+) was determined experimentally to be localized on the dioxolene bridge with a small amount of spin density on the outer phenolate moieties predicted by the calculations. This assignment was aided via comparison to data for the Ni analogue (Inorg. Chem., 2011, 50, 6746). The resonance Raman spectrum of [1˙](+) (λ(ex) = 413 nm) in CH(2)Cl(2) solution clearly exhibited a new band at 1308 cm(-1) in comparison to 1, supporting semiquinone formation. Variable-temperature EPR on the three-spin system [1˙](+) did not provide definitive information on the coupling interaction, possibly due to a very small difference in energy between the S = 3/2 and S = 1/2 states and/or a very small zero-field splitting, in combination with significant line-broadening. The data is consistent with a description of the overall electronic structure of [1˙](+) as a bimetallic Cu(II) complex with a bridge-localized semiquinone ligand radical species.