Polyhedral and Macropolyhedral Metal-Rich Cobaltaboranes: A 25-Vertex Hourglass-Shaped Cluster.

In an effort to break the single-cage 16-vertex supraicosahedral barrier, we have explored the reaction of [Cp*CoCl2], 1 with [LiBH4·THF], followed by thermolysis with [BH3·SMe2] [Cp* = η5-C5Me5]. Although our objective to synthesize a high-nuclearity single-cage cluster was not achieved, we have isolated a 25-vertex macropolyhedral cluster [(Cp*Co)5Co2B18H17(CH3)S] (2). Cluster 2 is an exceptional fused hourglass-shaped macropolyhedral cluster composing two icosahedral cores ([Co3B9] and [Co4B8]) and three tetrahedral cores [Co2B2]. Although the fusion in cluster 2 is very complex, it follows Mingos fusion formalism, leading to an attractive hourglass-shaped cluster. Through subtle changes in reaction conditions, two new cobaltaborane clusters, nido-4,5,7-[(Cp*Co)3B7H11] (3) and nido-2,9-[(Cp*Co)2B8H12] (4), have been isolated. The observed core geometries of clusters 3 and 4 are similar to the parent deltahedra [B10H14] with (n + 2) SEP (SEP = skeletal electron pair, n = no. of vertices). All the synthesized cobaltaboranes have been characterized in solution by ESI-mass, nuclear magnetic resonance spectroscopy, infrared spectroscopy and structurally solved by single-crystal X-ray diffraction analysis.

Hetero-trimetallic complexes comprising bridging boryl and borylene ligands: an experimental and theoretical study.

In an effort to explore the coordination chemistry of the coordinative sulfur centers in arachno-ruthenaborane [(Cp*Ru)2(B3H8)(CS2H)] (arachno-1), we have thermolyzed arachno-1 with group-6 metal carbonyls [M(CO)5·THF] (M = Cr, Mo and W). The reaction of arachno-1 with [Cr(CO)5·THF] resulted in the formation of hetero-trimetallic triply bridging borylene [(Cp*Ru)2(µ-CO)(µ3-CH2S2-κ2S':κ2S''){Cr(CO)3}(µ3-BH)] (2), bridging boryl-borylene [(Cp*Ru)2(µ-CO){(µ3-BH(CH2S2)-κ2B:κ2S':κ1S'')}{Cr(CO)3}(µ3-BH)] (3), and sulfido bridged hetero-trimetallic complex [(Cp*Ru)2(µ-CO)3{Cr(CO)3}(µ3-S)] (4). In 2, one side of Ru2Cr-triangle features a µ3-BH ligand while the other side is quadruply bridged by a methanedithiolato ligand in an unsymmetrical fashion. Unlike 2, in complex 3, one side of the Ru2Cr-triangle has a µ3-BH ligand while the opposite side is bridged by a boryl ligand BH(CH2S2) in an unsymmetrical way (µ3-κ2:κ2:κ1) to the metal centers. Interestingly, when the similar reactions of arachno-1 were performed with heavier group-6 metal carbonyls [M(CO)5·THF] (M = Mo and W), it led to the formation of methanedithiolato bridged hetero-trimetallic chain complexes, [{Cp*Ru(CO)}2(µ-CO)2(µ3-CH2S2-κ2S':κ2S''){M(CO)2}] (5, M = Mo; 6, M = W) and sulfido-bridged hetero-trimetallic complexes [(Cp*Ru)2(µ-CO)3{M(CO)3}(µ3-S)] (7, M = Mo; 8, M = W), analogous to 4. In complexes 5 and 6, a Ru2M-chain is symmetrically bridged by a methanedithiolato ligand. On the other hand, in complexes 4, 7, and 8, a sulfido ligand coordinates to two ruthenium and one group-6 metal atoms in µ3-fashion. All the complexes have been characterized by 1H NMR, 13C NMR, UV-vis, IR spectroscopy, and mass spectrometry and their structural architectures have been unambiguously established by single crystal X-ray diffraction studies. In addition, theoretical investigations provided valuable insights into their electronic structures and bonding properties.

Progress in Electrochemically Empowered C-O Bond Formation: Unveiling the Pathway of Efficient Green Synthesis.

(C-X) bonds (X=C, N, O) are the main backbone for making different skeleton in the organic synthetic transformations. Among all the sustainable techniques, electro-organic synthesis for C-X bond formation is the advanced tool as it offers a greener and more cost-effective approach to chemical reactions by utilizing electrons as reagents. In this review, we want to explore the recent advancements in electrochemical C-O bond formation. The electrochemically driven C-O bond formation represents an emerging and exciting area of research. In this context, electrochemical techniques offers numerous advantages, including higher yields, cost-efficient production, and simplified work-up procedures. This method enables the continuous and consistent formation of C-O bonds in molecules, significantly enhancing overall reaction yields. Furthermore, both intramolecular and intermolecular C-O bond forming reaction provided valuable products of O-containing acyclic/cyclic analogue. Hence, carbonyl (C=O), ether -O-), and ester (-COOR) functionalization in both cyclic/acyclic analogues have been prepared continuously via this innovative pathway. In this context, we want to discuss one-decade electrochemical synthetic pathways of various C-O bond contains functional group in chronological manner. This review focused on all the synthetic aspects including mechanistic path and has also mentioned overall critical finding regarding the C-O bond formation via electrochemical pathways.

Preparation and electrochemical characterization of polyaniline functionalized copper bridges carbon nanotube for supercapacitor applications.

Supercapacitor is an alternative power source due to its high energy density, fast charge/discharge time, low level of heating, safety, long-term operation stability. MWCNTs are used for supercapacitor applications due to their unique properties, structure, high surface area. In the present work nanocomposites were prepared from Cu modified MWCNTs (binary) from which ternary composite also prepared with HCI doped polyaniline (PANI). Cu modified MWCNTs were prepared by the reduction of copper sulphate with sodium borohydride in basic medium. The uniform coating of polymer, upon the Cu modified MWCNTs, was evidenced from the field emission scanning electron microscopic (FESEM) and high resolution transmission electron microscopic (HRTEM) images. The modification of MWCNTs with Cu, was confirmed from the X-ray Diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. Cyclic voltammetry (CV) measurement and charge discharge test shows higher capacitance for the ternary composites (264 F/g) compared to the binary system (125 F/g). The cyclic stability and retention of specific capacitance also shows the better result for ternary system.

α MnMoO4/graphene hybrid composite: high energy density supercapacitor electrode material.

A unique and cost effective hydrothermal procedure has been carried out for the synthesis of hexahedron shaped α MnMoO4 and its hybrid composite with graphene using three different weight percentages of graphene. Characterization techniques, such as XRD, Raman and FTIR analysis, established the phase and formation of the composite. The electrochemical characterization of the pseudocapacitive MnMoO4 and the MnMoO4/graphene composites in 1 M Na2SO4 displayed highest specific capacitances of 234 F g(-1) and 364 F g(-1), respectively at a current density of 2 A g(-1). Unlike many other pseudocapacitive electrode materials our prepared materials responded in a wide range of working potentials of (-)1 V to (+)1 V, which indeed resulted in a high energy density without substantial loss of power density. The highest energy densities of 130 Wh kg(-1) and 202.2 Wh kg(-1) were achieved, respectively for the MnMoO4 and the MnMoO4/graphene composite at a constant power delivery rate of 2000 W kg(-1). The synergistic effect of the graphene with the pseudocapacitive MnMoO4 caused an increased cycle stability of 88% specific capacitance retention after 1000 consecutive charge discharge cycles at 8 A g(-1) constant current density, which was higher than the virgin MnMoO4 with 84% specific capacitance retention.

Synthesis, characterization and electrochemical performance of graphene decorated with 1D NiMoO4 · nH2O nanorods.

One-dimensional NiMoO4 · nH2O nanorods and their graphene based hybrid composite with good electrochemical properties have been synthesized by a cost effective hydrothermal procedure. The formation of the mixed metal oxide and the composite was confirmed by XRD, XPS and Raman analyses. The morphological characterizations were carried out using FESEM and TEM analyses. The materials were subjected to electrochemical characterization through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) studies with 6 M KOH as the supporting electrolyte. For NiMoO4 · nH2O, a maximum specific capacitance of 161 F g(-1) was obtained at 5 A g(-1) current density, accompanied with an energy density of 4.53 W h kg(-1) at a steady power delivery rate of 1125 W kg(-1). The high utility of the pseudocapacitive NiMoO4 · nH2O was achieved in its graphene based composite, which exhibited a high specific capacitance of 367 F g(-1) at 5 A g(-1) current density and a high energy density of 10.32 W h kg(-1) at a power density of 1125 W kg(-1) accompanied with long term cyclic stability.

One pot synthesis of ilmenite-type NiMnO3-"nitrogen-doped" graphene nanocomposite as next generation supercapacitors.

NiMnO3-nitrogen doped graphene composite has been synthesized by a simple hydrothermal method and its supercapacitor performance investigated. The composite exhibits a specific capacitance of 750.2 F g(-1) in 1 M Na2SO4 at a scan rate of 1 mV s(-1). Nitrogen insertion inside the carbon lattice plays a crucial role in the enhancement of the overall specific capacitance and its long-term stability. This reproducible and superior performance of NiMnO3-nitrogen doped graphene composite make it attractive as a candidate for energy storage materials.