Ligand redox controlled amine dehydrogenation and imine hemilability in singlet diradical azo-aromatic Ni(II) complexes: characterization of the electron transfer series of azo-imine complexes of Ni(II).

Herein, using azo-amine (H2L) and azo-imine (L1-3) ligands, singlet diradical Ni(II) complexes [1] and [2] were synthesized from Ni(0)(COD)2 in THF. In separate reactions, homoleptic NiII complexes, [3a]2+-[3c]2+, were synthesized from [NiII(H2O)6](ClO4)2 and L1-3, respectively. All these complexes were characterized thoroughly. The X-ray structures of [1] and [2] showed that the amine side arm in [1] and the imine side arm in [2] are de-coordinated. The dN-N lengths in these two complexes were found to be ∼1.32 Å, which corresponds to the one-electron reduced azo-bond length. These complexes, [1] and [2], showed 1H NMR signals characteristic of diamagnetic compounds. These studies, along with DFT calculations, indicated that the unpaired spins on ligands coupled antiferromagnetically with the two unpaired spins on NiII to result in s = 0 ground states. Complex [1] showed ligand-based redox-induced dehydrogenation of the distal amine side arm to result in L1. Complexes [3a]2+-[3c]2+ have dN-N lengths of ∼1.27 Å and dC-N lengths of ∼1.28 Å. In cyclic voltammetry, complex [3a]2+ showed four well-resolved reversible reductive waves at 0.5 V to -1.6 V in dichloromethane. The first two waves became irreversible when they were measured in acetonitrile solution. The electron transfer series of [3a]2+ was further characterized by spectro-electrochemistry, EPR, and DFT calculations. These showed that all the reductions were associated with the ligand. It was further probed by redox events in complexes [3b]2+ and [3c]2+. While the electron donor -OMe group on the phenyl ring of the azo moiety in [3b]2+ showed a prominent cathodic shift of the potentials, the -F substitution on the phenyl group on the imine side arm of [3c]2+ has almost no effect. It has to be noted here that the oxidation of [2] by two electrons returns it back to complex [3a]2+. Reduction of [3a]2+ by two electrons also resulted in complex [2], indicating reversible ligand redox-induced hemilability of the imine moiety between [3a]2+ and [2]. Moreover, characterization of the electron transfer series of [3a]2+ and [2] has shown superior redox non-innocent behaviour and coordination ability of the azo-pyridine moiety in nickel(II) complexes over the imino-pyridine moiety of the ligand.

A Phosphine-Oxide Cobalt(II) Complex and Its Catalytic Activity Studies toward Alcohol Dehydrogenation Triggered Direct Synthesis of Imines and Quinolines.

Herein, a new pincer-like amino phosphine donor ligand, H2L1, and its phosphine-oxide analog, H2L2, were synthesized. Subsequently, cobalt(II) complexes 1 and 2 were synthesized by the reaction of anhydrous Co(II)Cl2 with ligands H2L1 and H2L2, respectively. The ligands and complexes were fully characterized by various physicochemical and spectroscopic characterization techniques. Finally, the identity of the complexes 1 and 2 was confirmed by single crystal X-ray structure determination. The phosphine ligand containing complex 1 was converted to the phosphine oxide ligand containing complex 2 in air in acetonitrile solution. Both complexes 1 and 2 were investigated as precatalysts for alcohol dehydrogenation-triggered synthesis of imines in air. The phosphine-oxide complex 2 was more efficient than the phosphine complex 1. A wide array of alcohols and amines were successfully reacted in a mild condition to result in imines in good to excellent yields. Precatalyst 2 was also highly efficient for the synthesis of varieties of quinolines in air. As H2L2 in 2 has side arms that can be deprotonated, we investigated complex 2 for its base (KOtBu) promoted deprotonation events by various spectroscopic studies and DFT calculations. These studies have shown that mono deprotonation of the amine side arm attached to the pyridine is quite feasible, and deprotonation of complex 2 leads to a dearomatized pyridyl ring containing complex 2a. The mechanistic investigations of the catalytic reaction, by a combination of experimental and computational studies, have suggested that the dearomatized complex, 2a acted as an active catalyst. The reaction proceeded through the hydride transfer pathway. The activation barrier of this step was calculated to be 26.5 kcal/mol, which is quite consistent with the experimental reaction temperature under aerobic conditions. Although various pincer-like complexes are explored for such reactions, phosphine oxide ligand-containing complexes are still unexplored.

Completely o-Phenylene Bridged N4-Cyclophane: A Missing Link in the Phenylene Bridge N4-Cyclophane Family.

Unprecedented types of metal-free complete o-phenylene bridged N4-cyclophanes (M1 and M2) have been synthesized via sequential palladium-catalyzed Buchwald-Hartwig N-arylation reactions. These cyclophanes may be considered as aromatic analogues of aliphatic group-spaced N4-macrocycles. These have been characterized fully using physicochemical characterization techniques and finally by single crystal X-ray structure determination. Their redox and spectral properties have been characterized by cyclic voltammetry, UV-vis spectro-electrochemistry, fluorescence spectral studies, and DFT calculations. These studies have shown rich redox, spectral, and photophysical properties that could make both M1 and M2 potential candidates for various applications.

Alcohol Dehydrogenation-Triggered Selective C3-Alkylation of Indoles by Homogeneous Azo-aromatic Cobalt Catalysts.

Herein, we report azo-benzimidazole containing cobalt complexes (1-3) for alcohol dehydrogenation-triggered C3-alkylation of indoles. In complexes 1-3, ligands are redox noninnocent and showed facile irreversible L/L• reduction followed by Co(II)/Co(I) reduction in close-lying potentials. Taking advantage of facile redox events in 1-3, the first aerial dehydrogenation of alcohols to their corresponding carbonyl compounds is explored. Subsequently, C3-alkylation of indole was studied using alcohols as the alkylating agents. The developed catalytic protocol was found to be efficient and very selective. It has a broad substrate scope and good functional group tolerance. As far as we are aware, it is the first homogeneous cobalt catalyst for C3-alkylation of indole using alcohol as the alkylating agent. Detailed mechanistic studies, including a deuterium labeling experiment, have suggested a borrowing hydrogen method for the C3-alkylation of indole. The coordinated ligand, cooperatively with the Co(II)/Co(I) redox couple, oxidized the coordinated alkoxide in a radical pathway to result in the carbonyl compound (Scheme 1), which on subsequent condensation with indole generates the alkylideneindolenine intermediate "X". Reduction of "X" by an azo-anion radical Co(I) catalyst intermediate resulted in the C3-alkylated indole.

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.

Polymerisation of styrene using pincer type amine functionalized azo aromatic complexes of Co(II) as catalysts.

In the present report, three mononuclear azo-aromatic complexes of Co(II), 1-3, and an imine-based Co(II) complex, 4, were synthesized through a reaction of respective amine-functionalized pincer-like ligands, HL1-4, with CoCl2·6H2O in the ligand-to-metal ratio of 1 : 1. All the complexes, 1-4, were thoroughly characterized using various physicochemical characterization techniques, single-crystal X-ray structure determination, and density functional theory (DFT) calculations. Complexes 1-4 were explored for the catalytic styrene polymerisation reaction separately in the presence of modified methyl aluminoxane (MMAO). All the complexes, 1-4, are indeed active for the polymerisation of styrene under mild conditions at room temperature upon activation with MMAO. Among the azo-aromatic complexes 1-3, complex 3 is the most efficient. The activity of the imine complex 4 is poor compared to those of the azo-aromatic complexes 1-3. The weight average molecular weight (Mw) of the isolated polystyrene ranges from 32.9 to 144.0 kg mol-1, with a polydispersity index (D) in the range of 1.1-1.8. Microstructural analysis of the isolated polymer from complexes 1-4 was carried out by 13C NMR spectroscopy, infrared spectroscopy, and powder X-ray diffraction studies. Their thermal properties were scrutinized by differential scanning calorimetry and thermogravimetric analysis. These studies have shown the atactic and amorphous nature of the polymers. The mechanical strength of the polymers was measured by a nanoindentation technique which has shown the good plastic/soft nature of the polymers.

Azide-Alkyne "Click" Reaction in Water Using Parts-Per-Million Amine-Functionalized Azoaromatic Cu(I) Complex as Catalyst: Effect of the Amine Side Arm.

A series of Cu(II) complexes, 1-4 and 6, were synthesized through a reaction of amine-functionalized pincer-like ligands, HL1,2, La,b, and a bidentate ligand L1 with CuCl2·2H2O. The chemical reduction of complex 1 using 1 equiv of sodium l-ascorbate resulted in a dimeric Cu(I) complex 5 in excellent yield. All of the complexes, 1-6, were thoroughly characterized using various physicochemical characterization techniques, single-crystal X-ray structure determination, and density functional theory calculations. Ligands HL1,2 and La,b behaved as tridentated donors by the coordination of the amine side arm in their respective Cu(II) complexes, and the amine side arm remained as a pendant in Cu(I) complexes. All of these complexes (1-6) were explored for copper(I)-catalyzed 1,3-dipolar azide-alkyne cycloaddition (CuAAC) reaction at room temperature in water under air. Complex 5 directly served as an active catalyst; however, complexes 1-4 and 6 required 1 equiv of sodium l-ascorbate to generate their corresponding active Cu(I) catalyst. It has been observed that azo-based ligand-containing Cu(I)-complexes are air-stable and were highly efficient for the CuAAC reaction. The amine side arm in the ligand backbone has a dramatic role in accelerating the reaction rate. Mechanistic investigations showed that the alkyne C-H deprotonation was the rate-limiting step and the pendant amine side arm intramolecularly served as a base for Cu-coordinated alkyne deprotonation, leading to the azide-alkyne 2 + 3 cycloaddition reaction. Thus, variation of the amine side arm in complexes 1-4 and use of the most basic diisopropyl amine moiety in complex 4 has resulted in an unique amine-functionalized azoaromatic Cu(I) system for CuAAC reaction upon sodium l-ascorbate reduction. The complex 4 has shown excellent catalysis at its low parts-per-million level loading in water. The catalytic protocol was versatile and exhibited very good functional group tolerance. It was also employed efficiently to synthesize a number of useful functional triazoles having medicinal, catalytic, and targeting properties.

Irreversible Resistive State Switching in Devices with a Homoleptic Cobalt(II) Complex Active Layer.

Molecules with bi-stable electronic transport behaviour have been in upfront research topics of the molecular semiconductor devices in the past few decades due to the use of such materials in resistive data storage devices. Transition metal complexes (TMC) are expected to be potential candidates in regard to the tunable and manifold redox behaviour expecting multiple bulk transport states. Finding alternate mechanisms in such devices with TMC as the active layer materials would revoke the multifaceted approach to the functional gain. We have succeeded in demonstrating write once-read many (WORM) type of resistive memory device using a homoleptic Cobalt(II) (Co(II)) complex with large on/off current ratio ensuring the easy readout process at lower voltage. The advantage of this device was the turn on voltage was found to be the low (<2.7 V) operational voltage and the success ratio of the devices were more than 83%. The durability of the stored data was found to be more than 35,000 seconds which ensures the stability of the bistable state in the fabricated devices. Such ambient stable, solution processable devices are important for the large-scale printable devices. The manuscript describes the preparation, optical and electrochemical characterisation of the metal complex used along with a detailed mechanistic investigations and electrical characterisation of memory device obtained from a stable cobalt complex.

Microwave-Assisted Neat Synthesis of a Ferrocene Appended Phenolphthalein Diyne: A Designed Synthetic Scaffold for Hg2+ Ion.

A C2-symmetric internally conjugated 1,3-dialkyne system 5, containing phenolphthalein as a fluorophore and ferrocene as a redox moiety, has been synthesized via a microwave-assisted synthetic procedure. Compound 5 was synthesized by Cu-catalyzed Glaser-Hay coupling using a microwave reactor in neat condition for the first time. Compound 5 was found to be highly selective toward Fe3+, Cu2+, and Hg2+ ions via multichannels. Interestingly, Fe3+ and Cu2+ ions simply promote the oxidation of ferrocene unit to ferrocenium ion without binding to the receptor, whereas Hg2+ binds with the receptor 5 (ΔE1/2 = 71 mV). The oxidation and binding phenomena were investigated by optical and electrochemical analyses. Furthermore, the binding site of Hg2+ ion with our designed probe was confirmed by 1H, 13C NMR and IR titrations, which indicated that conjugated dialkyne unit interacts with Hg2+ ion by a favorable soft-soft interaction. Both receptor 5 and its metal complex, [5·2Hg2+], are stable in the physiological pH range (pH = 6-7) and thermally stable up to 78 °C. The experimental results of metal binding have been further supported by quantum chemical calculations (DFT), which explore the favorable geometry of the free ligand as well as its Hg2+ complex.

Dehydrogenation of amines in aryl-amine functionalized pincer-like nitrogen-donor redox non-innocent ligands via ligand reduction on a Ni(ii) template.

We have synthesized a series of new redox non-innocent azo aromatic pincer-like ligands: 2-(phenylazo)-6-(arylaminomethyl)pyridine (HLa-c: HLa = 2-(phenylazo)-6-(2,6-diisopropylphenylaminomethyl)pyridine, HLb = 2-(phenylazo)-6-(2,6-dimethylphenylaminomethyl)pyridine, and HLc = 2-(phenylazo)-6-(phenylaminomethyl)pyridine), in which one side arm is an arylaminomethyl moiety and the other arm is a 2-phenylazo moiety. Nickel(ii) complexes, 1-3, of these ligands HLa-c were synthesized in good yield (approximately 70%) by the reaction of ligands : (NiCl2·6H2O) in a 1 : 1 molar ratio in methanol. The amine donor in each of the ligands HLa-c binds to the Ni(ii) centre without deprotonation. In the solid state, complex 3 is a dimer; in solution it exists as monomer 3a. The reduction of acetonitrile solutions of each of the complexes 1, 2 and 3a, separately, with cobaltocene (1 equivalent), followed by exposure of the solution to air, resulted in the formation of new complexes 7, 8 and 9, respectively. Novel free ligands Lx and Ly have also been isolated, in addition to complexes 7 and 8, from the reaction of complexes 1 and 2, respectively. Complexes 7-9 and free ligands Lx and Ly have been formed via a dehydrogenation reaction of the arylaminomethyl side arm. The mechanism of the reaction was thoroughly investigated using a series of studies, including cyclic voltammetry, EPR, and UV-Vis spectral studies and density functional theory (DFT) calculations. The results of these studies suggest a mechanism initiated by ligand reduction followed by dioxygen activation. A Cl-/I- scrambling experiment revealed that the dissociation of the chloride ligand(s) was associated with the one-electron reduction of the ligand (azo moiety) in each of the complexes 1, 2 and 3a. The dissociated chloride ligand(s) were reassociated with the metal following the dehydrogenation reaction to yield the final products. All of the newly synthesized compounds were fully characterized using a variety of physicochemical techniques. Single-crystal X-ray structures of the representative compounds were determined to confirm the identities of the synthesized molecules.