A bioinspired cobalt catalyst based on a tripodal imidazole/pyridine platform capable of water reduction and oxidation.

The prototypical drug carrier [CoII(L1)Cl]PF6 (1), where L1 is a tripodal amine bound to pyridine and methyl-imidazoles, had its electrocatalytic water splitting activity studied under different pH conditions. This species contains a high-spin 3d7 CoII metal center, and is capable of generating both H2 from water reduction and O2 from water oxidation. Turnover numbers reach 390 after 3 h for water reduction. Initial water oxidation activity is molecular, with TONs of 71 at pH 7 and 103 at pH 11.5. The results reveal that species 1 can undergo several redox transformations, including reduction to the 3d8 CoI species that precedes a LS3d6 hydride for water reduction, as well as nominal CoIVO and CoIII-OOH species required for water oxidation. Post-catalytic analyses confirm the molecular nature of reduction and support initial molecular activity for oxidation.

Hemilabile Amine-Functionalized Efficient Azo-Aromatic Cu-Catalysts Inspired by Galactose Oxidase: Impact of Amine Sidearm on Catalytic Aerobic Oxidation of Alcohols.

A series of azo-aromatic copper(II) complexes, [1a-g] and a Cu(I) complex, [1h], with varying amine-functionalized hemilabile pincer-like [HL1-3] and [L1,2], methyl-substituted azo [L3], and imine [L4] ligands, were synthesized and characterized. These complexes were investigated for aerobic oxidation of a variety of aromatic alcohols in the presence of 2.0 mol % precatalysts [1a-g], cobaltocene (2.0 mol %), N-methyl imidazole (NMI) (8.0 mol %), and TEMPOH (2.0 mol %) at room temperature. The Cu(I) complex (1h) acted as a catalyst in the absence of cobaltocene. To understand the mechanism, detailed experimental and theoretical studies have been performed with the representative complex [1a], which has suggested a new kind of mechanism involving a Cu(II)/Cu(I) redox couple. Cobaltocene acts as a reductant to [1a] to generate a Cu(I) complex, which activates dioxygen in the presence of NMI. TEMPOH transfers a hydrogen atom to the activated dioxygen with the generation of TEMPO•, which further participates in α-C-H bond activation in the Cu(II)-alkoxide intermediate in an intermolecular fashion in the catalytic cycle. The amine sidearm in the ligand backbone of the complexes has a significant role in catalytic activity. Complexes with amine sidearms are more effective than complexes without them. Moreover, the aliphatic secondary amine sidearm is more efficient among the amine sidearm than the aromatic secondary amine and tertiary amines. The amine sidearm that remained coordinated to the Cu(II) center is hemilabile, and it facilitates alcohol coordination in the catalytic process. Alcohol coordination was the rate-limiting step, and it was supported by the isotope effect study on benzyl alcohol, substitution effect on the amine moiety of the ligands, and DFT calculation. The hemilabile amine sidearm of the coordinated ligand also acted as a base in deprotonating the alcoholic O-H proton and acted as an acid in releasing H2O2 during the catalysis.

Reactivity and Mechanisms of Photoactivated Heterometallic [RuII NiII ] and [RuII NiII RuII ] Catalysts for Dihydrogen Generation from Water.

Two heterometallic photocatalysts were designed and probed for water reduction. Both [(bpy)2 RuII NiII (L1 )](ClO4 )2 (1) and [(bpy)2 RuII NiII (L2 )2 RuII (bpy)2 ](ClO4 )2 (2) can generate the low-valent precursor involved in hydride formation prior to dihydrogen generation. However, while the bimetallic [RuII NiII ] (1) requires the presence of an external photosensitizer to trigger catalytic activity, the trimetallic [RuII NiII RuII ] (2) displays significant coupling between the catalytic and light-harvesting units to promote intramolecular multielectron transfer and perform photocatalysis at the Ni center. A concerted experimental and theoretical effort proposes mechanisms to explain why 1 is unable to achieve self-supported catalysis, while 2 is fully photocatalytic.

Influence of nitro substituents on the redox, electronic, and proton reduction catalytic behavior of phenolate-based [N2O3]-type cobalt(iii) complexes.

We report on the synthesis, redox, electronic, and catalytic behavior of two new cobalt(iii) complexes, namely [CoIII(L1)MeOH] (1) and [CoIII(L2)MeOH] (2). These species contain nitro-rich, phenolate-based pentadentate ligands and present dramatically distinct properties associated with the position in which the -NO2 substituents are installed. Species 1 displays nitro-substituted phenolates, and exhibits irreversible redox response and negligible catalytic activity, whereas 2 has fuctionalized phenylene moieties, shows much improved redox reversibility and catalytic proton reduction activity at low overpotentials. A concerted experimental and theoretical approach sheds some light on these drastic differences.

A pentadentate nitrogen-rich copper electrocatalyst for water reduction with pH-dependent molecular mechanisms.

The new pentadentate 3d9 complex [CuII(LN2Py3)](PF6)2 (1) based on a nitrogen-rich framework acts as an electrocatalyst toward dihydrogen production from water. This species is active at pHs 7 and 2.5 yielding respective TON3h values of 1670 and 3900. Comparison of the molecular structure of 1 with that of the reduced [CuI(LN2Py3)]PF6 (2) evidences elongated Cu-N bond lengths resulting from an increased electron density around the 3d10 CuI center. The absence of nanoparticulate formation indicates that molecular mechanisms prevail at both pHs. Furthermore, experimental and DFT data support that distinct mechanisms are operative: while the metal center plays a key role at pH 7, one dangling pyridine moiety gets protonated at pH 2.5 and becomes actively involved in a relay mechanism. In both cases the CuIII-H- intermediate seems to be bypassed by PCET processes.

Bimetallic Cooperativity in Proton Reduction with an Amido-Bridged Cobalt Catalyst.

The bimetallic catalyst [CoII2 (L1 )(bpy)2 ]ClO4 (1), in which L1 is an [NN'2 O2 ] fused ligand, efficiently reduced H+ to H2 in CH3 CN in the presence of 100 equiv of HOAc with a turnover number of 18 and a Faradaic efficiency of 94 % after 3 h of bulk electrolysis at -1.6 V (vs. Ag/AgCl). This observation allowed the proposal that this bimetallic cooperativity is associated with distance, angle, and orbital alignment of the two Co centers, as promoted by the unique Co-Namido -Co environment offered by L1 . Experimental results revealed that the parent [CoII CoII ] complex undergoes two successive metal-based 1 e- reductions to generate the catalytically active species [CoI CoI ], and DFT calculations suggested that addition of a proton to one CoI triggers a cooperative 1 e- transfer by each of these CoI centers. This 2 e- transfer is an alternative route to generate a more reactive [CoII (CoII -H- )] hydride, thus avoiding the CoIII -H- required in monometallic species. This [CoII (CoII -H- )] species then accepts another H+ to release H2 .

Deactivation of a Cobalt Catalyst for Water Reduction through Valence Tautomerism.

The activity of the water reduction catalyst [CoIII (L1 )(pyr)2 ]PF6 (1), where (L1 )2- is a bis-amido pyridine ligand and pyr is pyrrolidine, is investigated. Catalyst 1 has an overpotential of 0.54 V and a high observed TOF of 23 min-1 , albeit for a relatively short time. Considering the significant activity of 1 and aiming to improve catalyst design, a detailed structural and electronic study is performed to understand the mechanisms of deactivation. Experimental and theoretical evidence support that the metal-reduced [CoI (L1 )]- is in tautomeric equilibrium with the ligand-reduced [CoII (L1. )]- species. While [CoI (L1 )]- favors formation of a CoIII -H- relevant for catalysis, the [CoII (L1. )]- species leads to ligand protonation, structural distortions, and, ultimatley, catalyst deactivation.

Efficient electro/photocatalytic water reduction using a [NiII(N2Py3)]2+ complex.

The pyridine-rich complex [NiII(LN2Py3)(MeCN)](ClO4)2 (1) acts as an efficient electro- and photocatalyst in the generation of H2 from water. Observed TONs reach 1050 for electrocatalysis and a remarkable 3500 for photocatalysis. Experimental and DFT data support the ligand-reduced [NiIL˙] as the catalytically active species, contrasting with the [CoIL] observed for cobalt catalysts.

Are Very Small Emission Quantum Yields Characteristic of Pure Metal-to-Ligand Charge-Transfer Excited States of Ruthenium(II)-(Acceptor Ligand) Chromophores?

Metal to ligand charge-transfer (MLCT) excited state emission quantum yields, ϕem, are reported in 77 K glasses for a series of pentaammine and tetraammine ruthenium(II) complexes with monodentate aromatic acceptor ligands (Ru-MDA) such as pyridine and pyrazine. These quantum yields are only about 0.2-1% of those found for their Ru-bpy (bpy = 2,2'-bipyridine) analogs in similar excited state energy ranges (hνem). The excited state energy dependencies of the emission intensity are characterized by mean radiative decay rate constants, kRAD, resolved from ϕem/τobs = kRAD (τobs = the observed emission decay lifetime; τobs(-1) = kRAD + kNRD; kNRD = nonradiative decay rate constant). Except for the Ru-pz chromophores in alcohol glasses, the values of kNRD for the Ru-MDA chromophores are slightly smaller, and their dependences on excited state energies are very similar to those of related Ru-bpy chromophores. In principle, one expects kRAD to be proportional to the product of (hνem)(3) and the square of the transition dipole moment (Me,g).(2) However, from experimental studies of Ru-bpy chromophores, an additional hνem dependence has been found that originates in an intensity stealing from a higher energy excited state with a much larger value of Me,g. This additional hνem dependence is not present in the kRAD energy dependence for Ru-MDA chromophores in the same energy regime. Intensity stealing in the phosphorescence of these complexes is necessary since the triplet-to-singlet transition is only allowed through spin-orbit coupling and since the density functional theory modeling implicates configurational mixing between states in the triplet spin manifold; this is treated by setting Me,g equal to the product of a mixing coefficient and the difference between the molecular dipole moments of the states involved, which implicates an experimental first order dependence of kRAD on hνem. The failure to observe intensity stealing for the Ru-MDA complexes suggests that their weak emissions are more typical of "pure" (or unmixed) (3)MLCT excited states.

Effects of Methyl Substitution in Ruthenium Tris(2-pyridylmethyl)amine Photocaging Groups for Nitriles.

Four complexes of the general formula [Ru(L)(CH3CN)2](PF6)2, [L = TPA (5), MeTPA (6), Me2TPA (7), and Me3TPA (8)] [TPA = tris[(pyridin-2-yl)methyl]amine, where methyl groups were introduced consecutively onto the 6-position of py donors of TPA, were prepared and characterized by various spectroscopic techniques and mass spectrometry. While 5 and 8 were isolated as single stereoisomers, 6 and 7 were isolated as mixtures of stereoisomers in 2:1 and 1.5:1 ratios, respectively. Steric effects on ground state stability and thermal and photochemical reactivities were studied for all four complexes using (1)H NMR and electronic absorption spectroscopies and computational studies. These studies confirmed that the addition of steric bulk accelerates photochemical and thermal nitrile release.

Electronic Modulation of the SOMO-HOMO Energy Gap in Iron(III) Complexes towards Unimolecular Current Rectification.

Amphiphilic five-coordinate iron(III) complexes with {N2 O2 Cl} and {N2 O3 } coordination spheres are studied to elucidate the roles of electronic structure on the mechanisms for current rectification. The presence of an apical chlorido or phenolato ligand plays a crucial role, and the [Fe(III) {N2 O2 Cl}] species supports an asymmetric mechanism while its [Fe(III) {N2 O3 }] counterpart seems to allow for unimolecular mechanism. The effects of electron-donating and electron-withdrawing substituents in the ligand frameworks are also considered.

Evaluation of the coordination preferences and catalytic pathways of heteroaxial cobalt oximes towards hydrogen generation.

Three new heteroaxial cobalt oxime catalysts, namely [CoIII(prdioxH)(4tBupy)(Cl)]PF6 (1), [CoIII(prdioxH)(4Pyrpy)(Cl)]PF6 (2), and [CoIII(prdioxH)(4Bzpy)(Cl)]PF6 (3) have been studied. These species contain chloro and substituted tert-butyl/pyrrolidine/benzoyl-pyridino ligands axially coordinated to a trivalent cobalt ion bound to the N4-oxime macrocycle (2E,2'E,3E,3'E)-3,3'-(propane-1,3-diylbis(azanylylidene))bis(butan-2-one)dioxime, abbreviated (prdioxH)- in its monoprotonated form. Emphasis was given to the spectroscopic investigation of the coordination preferences and spin configurations among the different 3d6 CoIII, 3d7 CoII, and 3d8 CoI oxidation states of the metal, and to the catalytic proton reduction with an evaluation of the pathways for the generation of H2via CoIII-H- or CoII-H- intermediates by mono and bimetallic routes. The strong field imposed by the (prdioxH)- ligand precludes the existence of high-spin configurations, and 6-coordinate geometry is favored by the LSCoIII species. Species 1 and 3 show a split CoIII/CoII electrochemical wave associated with partial chemical conversion to a [CoIII(prdioxH)Cl2] species, whereas 2 shows a single event. The reduction of these CoIII complexes yields LSCoII and LSCoI species in which the pyridine acts as the dominant axial ligand. In the presence of protons, the catalytically active CoI species generates a CoIII-H- hydride species that reacts heterolytically with another proton to generate dihydrogen. The intermediacy of a trifluoroacetate-bound CoIII/CoII couple in the catalytic mechanism is proposed. These results allow for a generalization of the behavior of heteroaxial cobalt macrocycles and serve as guidelines for the development of new catalysts based on macrocyclic frameworks.

Selective Photodissociation of Acetonitrile Ligands in Ruthenium Polypyridyl Complexes Studied by Density Functional Theory.

Metal complexes that release ligands upon photoexcitation are important tools for biological research and show great potential as highly specific therapeutics. Upon excitation with visible light, [Ru(TQA)(MeCN)2](2+) [TQA = tris(2-quinolinylmethyl)amine] exchanges one of the two acetonitriles (MeCNs), whereas [Ru(DPAbpy)MeCN](2+) [DPAbpy = N-(2,2'-bipyridin-6-yl)-N,N-bis(pyridin-2-ylmethyl)amine] does not release MeCN. Furthermore, [Ru(TQA)(MeCN)2](2+) is highly selective for release of the MeCN that is perpendicular to the plane of the two axial quinolines. Density functional theory calculations provide a clear explanation for the photodissociation behavior of these two complexes. Excitation by visible light and intersystem crossing leads to a six-coordinate (3)MLCT state. Dissociation of acetonitrile can occur after internal conversion to a dissociative (3)MC state, which has an occupied dσ* orbital that interacts in an antibonding fashion with acetonitrile. For [Ru(TQA)(MeCN)2](2+), the dissociative (3)MC state is lower than the (3)MLCT state. In contrast, the (3)MC state of [Ru(DPAbpy)MeCN](2+) that releases acetonitrile has an energy higher than that of the (3)MLCT state, indicating dissociation is unfavorable. These results are consistent with the experimental observations that efficient photodissociation of acetonitrile occurs for [Ru(TQA)(MeCN)2](2+) but not for [Ru(DPAbpy)MeCN](2+). For the release of the MeCN ligand in [Ru(TQA)(MeCN)2](2+) that is perpendicular to the axial quinoline rings, the (3)MLCT state has an occupied quinoline π* orbital that can interact with a dσ* Ru-NCCH3 antibonding orbital as the Ru-NCCH3 bond is stretched and the quinolines bend toward the departing acetonitrile. This reduces the barrier for the formation of the dissociative (3)MC state, leading to the selective photodissociation of this acetonitrile. By contrast, when the acetonitrile is in the plane of the quinolines or bpy, no interaction occurs between the ligand π* orbital and the dσ* Ru-NCCH3 orbital, resulting in high barriers for conversion to the corresponding (3)MC structures and no release of acetonitrile.

Metal-to-Ligand Charge-Transfer Emissions of Ruthenium(II) Pentaammine Complexes with Monodentate Aromatic Acceptor Ligands and Distortion Patterns of their Lowest Energy Triplet Excited States.

This is the first report of the 77 K triplet metal-to-ligand charge-transfer ((3)MLCT) emission spectra of pentaammine-MDA-ruthenium(II) ([Ru(NH3)5(MDA)](2+)) complexes, where MDA is a monodentate aromatic ligand. The emission spectra of these complexes and of the related trans-[Ru(NH3)4(MDA) (MDA')](2+) complexes are closely related, and their emission intensities are very weak. Density functional theory (DFT) calculations indicate that the energies of the lowest (3)MLCT excited states of Ru-MDA complexes are either similar to or lower than those of the lowest energy metal-centered excited states ((3)MC(X(Y))), that the barrier to internal conversion at 77 K is large compared to kBT, and that the (3)MC(X(Y)) excited states are weakly bound. The [Ru(NH3)5py](2+) complex is an exception to the general pattern: emission has been observed for the [Ru(ND3)5(d5-py)](2+) complex, but its lifetime is apparently very short. DFT modeling indicates that the excited state distortions of the different (3)MC excited states are very large and are in both Ru-ligand bonds along a single Cartesian axis for each different (3)MC excited state, nominally resulting in (3)MC(X(Y)), (3)MC((X)Y), and (3)MC(Z) lowest energy metal-centered states. The (3)MC(X(Y)) and (3)MC((X)Y) states appear to be the pseudo-Jahn-Teller distorted components of a (3)MC((XY)) state. The (3)MC(X(Y)) states are distorted up to 0.5 Šin each H3N-Ru-NH3 bond along a single Cartesian axis in the pentaammine and trans-tetraammine complexes, whereas the (3)MC(Z) states are found to be dissociative. DFT modeling of the (3)MLCT excited state of [Ru(NH3)5(py)](2+) indicates that the Ru center has a spin density of 1.24 at the (3)MLCT energy minimum and that the (3)MLCT → (3)MC(Z) crossing is smooth with a very small barrier (<0.5 kcal/mol) along the D3N-Ru-py distortion coordinate, implying strong (3)MLCT/(3)MC excited state configurational mixing. Furthermore, the DFT modeling indicates that the long-lived intermediate observed in earlier flash photolysis studies of [Ru(NH3)5py](2+) is a Ru(II)-(η(2)(C═C)-py) species.

Distinct Proton and Water Reduction Behavior with a Cobalt(III) Electrocatalyst Based on Pentadentate Oximes.

A new pentadentate oxime has been designed to drive the preferential coordination favored by Co(I) in catalysts used for proton/water reduction. The ligand incorporates water upon metal coordination and is water soluble. This Co(III) species is doubly reduced to Co(I) and exhibits H(+) reduction activity in the presence of weak acids in MeCN and evolves H2 upon protonation suggesting that the ligand design increases catalyst effectiveness. Superior catalysis is observed in water with a turnover number (TON) of 5700 over 18 h. However, the catalyst yields Co-based nanoparticles, indicating that the solvent media may dictate the nature of the catalyst.

Energy Dependence of the Ruthenium(II)-Bipyridine Metal-to-Ligand-Charge-Transfer Excited State Radiative Lifetimes: Effects of ππ*(bipyridine) Mixing.

The variations in band shape with excited state energy found for the triplet metal to ligand charge transfer ((3)MLCT) emission spectra of ruthenium-bipyridine (Ru-bpy) chromophores at 77 K have been postulated to arise from excited state/excited state configurational mixing. This issue is more critically examined through the determination of the excited state energy dependence of the radiative rate constants (kRAD) for these emissions. Experimental values for kRAD were determined relative to known literature references for Ru-bpy complexes. When the lowest energy excited states are metal centered, kRAD can be anomalously small and such complexes have been identified using density functional theory (DFT) modeling. When such complexes are removed from the energy correlation, there is a strong (3)MLCT energy-dependent contribution to kRAD in addition to the expected classical energy cubed factor for complexes with excited state energies greater than 10 000 cm(-1). This correlates with the DFT calculations which show significant excited state electronic delocalization between a π(bpy-orbital) and a half-filled dπ*-(Ru(III)-orbital) for Ru-bpy complexes with (3)MLCT excited state energies greater than about 16 000 cm(-1). Overall, this work implicates the "stealing" of emission bandshapes as well as intensity from the higher energy, strongly allowed bpy-centered singlet ππ* excited state.

The origin of the ligand-controlled regioselectivity in Rh-catalyzed [(2 + 2) + 2] carbocyclizations: steric vs. stereoelectronic effects.

Density functional theory calculations demonstrate that the reversal of regiochemical outcome of the addition for substituted methyl propiolates in the rhodium-catalyzed [(2 + 2) + 2] carbocyclization with PPh3 and (S)-xyl-binap as ligands is both electronically and sterically controlled. For example, the ester functionality polarizes the alkyne π* orbital to favor overlap of the methyl-substituted terminus of the alkyne with the pπ-orbital of the alkenyl fragment of the rhodacycle during alkyne insertion with PPh3 as the ligand. In contrast, the sterically demanding xyl-binap ligand cannot accommodate the analogous alkyne orientation, thereby forcing insertion to occur at the sterically preferred ester terminus, overriding the electronically preferred orientation for alkyne insertion.

Ligand transformations and efficient proton/water reduction with cobalt catalysts based on pentadentate pyridine-rich environments.

A series of cobalt complexes with pentadentate pyridine-rich ligands is studied. An initial Co(II) amine complex 1 is prone to aerial oxidation yielding a Co(III) imine complex 2 that is further converted into an amide complex 4 in presence of adventitious water. Introduction of an N-methyl protecting group to the ligand inhibits this oxidation and gives rise to the Co(II) species 5. Both the Co(III) 4 and Co(II) 5 show electrocatalytic H2 generation in weakly acidic media as well as in water. Mechanisms of catalysis seem to involve the protonation of a Co(II)-H species generated in situ.

The mechanisms of rectification in Au|molecule|Au devices based on Langmuir-Blodgett monolayers of iron(III) and copper(II) surfactants.

Langmuir-Blodgett films of metallosurfactants were used in Au|molecule|Au devices to investigate the mechanisms of current rectification.

Switching the enantioselectivity in catalytic [4 + 1] cycloadditions by changing the metal center: principles of inverting the stereochemical preference of an asymmetric catalysis revealed by DFT calculations.

The mechanisms of the asymmetric [4 + 1] carbocyclization of vinylallenes with carbon monoxide catalyzed by Pt(0) and Rh(I) carrying the chiral support ligand (R,R)-Me-DuPHOS (Me-DuPHOS = 1,2-bis(2,5-dimethylphosphorano)benzene) were studied using density functional theoretical models. Previously, it was observed that the (R)-stereoisomer of the 5-substituted 2-alkylidene-3-cyclopentenone products was obtained with Pt(0), but the (S)-enantiomer was formed when Rh(I) metal was used to promote the reaction. Our calculations suggest that the rate-determining step in both cases consists of a C-C coupling between the vinyl end of the vinylallene substrate and carbon monoxide that is accompanied by charge transfer from the metal center to the organic substrate. The reason that the two metals give different enantiomer products lies in the very different geometries of the metal centers in the transition state. The platinum center adopts a square-planar geometry throughout the C-C coupling reaction, which forces the carbonyl to migrate from the metastable, pseudoaxial position into the equatorial plane. During this migration, the carbonyl encounters the spatial constraints caused by the asymmetric DuPHOS ligand, while the vinylallene fragment is pushed away from the metal center. Thus, regardless of the steric demands of the organic substrate, the transition state that places the vinyl in a position that allows the CO to move into the sterically less crowded side of the molecule is preferred. Rh, on the other hand, maintains a square-pyramidal geometry throughout the reaction, keeping the CO ligand at the axial coordination site. The C-C coupling is accomplished by pulling the vinylallene substate closer to the metal and, as a result, the transition state that causes the least amount of steric clashes between the substrate and the DuPHOS ligand is favored, which affords the (S)-enantiomeric product.