Monodisperse Molecular Models for the sp Carbon Allotrope Carbyne; Syntheses, Structures, and Properties of Diplatinum Polyynediyl Complexes with PtC20Pt to PtC52Pt Linkages.

Extended conjugated polyynes provide models for the elusive sp carbon polymer carbyne, but progress has been hampered by numerous synthetic challenges. Stabilities appear to be enhanced by bulky, electropositive transition-metal endgroups. Reactions of trans-(C6F5)(p-tol3P)2Pt(C≡C)nSiEt3 (n = 4-6, PtCxSi (x = 2n)) with n-Bu4N+F-/Me3SiCl followed by excess tetrayne H(C≡C)4SiEt3 (HC8Si) and then CuCl/TMEDA and O2 give the heterocoupling products PtCx+8Si, PtCx+16Si, and sometimes higher homologues. The PtCx+16Si species presumably arise via protodesilylation of PtCx+8Si under the reaction conditions. Chromatography allows the separation of PtC16Si, PtC24Si, and PtC32Si (from n = 4), PtC18Si and PtC26Si (n = 5), or PtC20Si and PtC28Si (n = 6). These and previously reported species are applied in similar oxidative homocouplings, affording the family of diplatinum polyynediyl complexes PtCxPt (x = 20, 24, 28, 32, 36, 40 in 96-34% yields and x = 44, 48, 52 in 22-7% yields). These are carefully characterized by 13C NMR, UV-visible, and Raman spectroscopy and other techniques, with particular attention to behavior as the Cx chain approaches the macromolecular limit and endgroup effects diminish. The crystal structures of solvates of PtC20Pt, PtC24Pt, and PtC26Si, which feature the longest sp chains structurally characterized to date, are analyzed in detail. All data support a polyyne electronic structure with a nonzero optical band gap and bond length alternation for carbyne.

Organosulphur, organoselenium and organotellurium compounds for the development of heterogeneous and nanocatalytic systems for Suzuki coupling.

Suzuki-Miyaura cross-coupling (SMC) is an extremely useful reaction in organic syntheses. During the last two decades, many researchers across the world have employed organochalcogen compounds in various ways for the development of catalytic systems for this reaction. Chalcogen-ligated molecular complexes have been designed using such compounds as ligands, and applied as homogeneous catalytic systems. During the period 2013-2022, various heterogeneous and nano-catalytic systems have also been developed using organosulphur, organoselenium and organotellurium compounds. The main advantages associated with such systems are their easy synthesis and air- and moisture-insensitivity. This article aims to provide insights into the synthetic methodologies pertaining to the preparation of (i) these catalytically relevant and useful compounds and (ii) the heterogeneous and nano-catalytic systems designed using them. Another major focus of the article is to rationalize and critically analyse the effect of chalcogen donor on the size, composition, morphology and shape of the nanostructure. A critical analysis of the applications of all such catalytic systems in Suzuki-Miyaura coupling is presented in detail. Various factors (e.g., temperature) which affect the catalytic performance are also rationalized. The effects of binding mode, ligand framework, chalcogen donor atom and metal are also covered, along with all other factors that influence the catalytic potential of the systems. Various other aspects such as green catalysis (in aqueous medium and in air), and use of non-conventional (ultrasonic radiation) energy sources are analysed. Applications of heterogeneous and nanocatalytic systems apart from Suzuki coupling are also highlighted, and challenges and future scope are elaborated.

Organosulphur and organoselenium compounds as emerging building blocks for catalytic systems for O-arylation of phenols, a C-O coupling reaction.

Diaryl ethers form an important class of organic compounds. The classic copper-mediated Ullmann diaryl ether synthesis has been known for many years and involves the coupling of phenols with aryl halides. However, the use of high reaction temperature, high catalyst loading and expensive ligands has created a need for the development of alternative catalytic systems. In the recent past, organosulphur and organoselenium compounds have been used as building blocks for developing homogeneous, heterogeneous and nanocatalysts for this C-O coupling reaction. Homogeneous catalytic systems include preformed complexes of metals with organosulphur and organoselenium ligands. The performance of such complexes is influenced dramatically by the nature of the chalcogen (S or Se) donor site of the ligand. Nanocatalytic systems (including Pd17Se15, Pd16S7 and Cu1.8S) have been designed using a single-source precursor route. Heterogeneous catalytic systems contain either metal (Cu or Pd) or metal chalcogenides (Pd17Se15 or Cu1.8S) as catalytically active species. This article aims to cover the simple and straightforward methodologies and approaches that are adopted for developing catalytically relevant organosulfur and organoselenium ligands, their homogeneous metal complexes, heterogeneous and nanocatalysts. The effects of chalcogen (S or Se) donor, halogen (Cl/Br/I) of aryl halide, nature (electron withdrawing or electron donating) of substituents present on the aromatic ring of aryl halides or substituted phenols and position (ortho or para) of substitution on the results of catalytic reactions have been critically analyzed and summarized. The effect of composition (Pd17Se15 or Pd16S7) on the performance of nanocatalytic systems is also highlighted. Substrate scope has also been discussed in all three types of catalysis. The superiority of heterogeneous catalytic systems (e.g., Pd17Se15 immobilised on graphene oxide) indicates the bright future possibilities for the development of efficient catalytic systems using similar or tailored ligands for this reaction.

Single source precursor route for the first graphene oxide-Pd6P nanocomposite: application in electrochemical hydrogen evolution reaction.

For the first time, Pd6P has been synthesised using a simple, straightforward and one-pot method i.e., thermolysis of a Pd(II) complex of a bidentate (P, N) organophosphorus ligand (anthracene-9-yl-CHN-CH2CH2-PPh2). The electrocatalyst (obtained after grafting nanospheres of Pd6P over layers of graphene oxide) shows high activity in electrochemical hydrogen evolution reactions (HER) with an overpotential of 133 mV to drive 10 mA cm-2 of cathodic current density. The GO-Pd6P nanocomposite is robust and effective for a continuous HER run for up to 16 hours.

Organoselenium ligands for heterogeneous and nanocatalytic systems: development and applications.

Organoselenium ligands have attracted great attention among researchers during the past two decades. Various homogeneous, heterogeneous and nanocatalytic systems have been designed using such ligands. Although reports on selenium ligated homogeneous catalysts are quite high in number, significant work has also been done on the development of heterogeneous and nanocatalytic systems using organoselenium ligands. A review article, focusing on the utility of organoselenium compounds in the development of catalytic systems, was published in 2012 (A. Kumar, G. K. Rao, F. Saleem and A. K. Singh, Dalton Trans., 2012, 41, 11949). Moreover, it mainly covered the homogeneous catalysts. There are no review articles in the literature on heterogeneous and nanocatalytic systems designed using organoselenium compounds and their applications. Hence, this perspective aims to cover the developments pertaining to the synthetic aspects of such catalytic systems (using organoselenium compounds) and their applications in catalysis of a variety of chemical transformations. Salient features and advantages of organoselenium compounds have also been highlighted to justify the rationale behind their use in catalyst development. Their performance in various chemical transformations [viz. Suzuki-Miyaura coupling, Heck coupling, Sonogashira coupling, O-arylation of phenol, transfer hydrogenation of aldehydes and ketones, aldehyde-alkyne-amine (A3) coupling, hydration of nitriles, conversion of aldehydes to amides, cross-dehydrogenative coupling (CDC), photodegradation of substrates (formic acid, methylene blue), reduction of nitrophenols, electrolysis (hydrogen evolution reaction and oxygen reduction reactions), organocatalysis and dye sensitized solar cells] and relevant aspects of catalytic processes (such as recyclability, substrate scope and green aspects) have been critically analyzed. Future perspectives have also been discussed.

Catalytically active nanosized Pd9Te4 (telluropalladinite) and PdTe (kotulskite) alloys: first precursor-architecture controlled synthesis using palladium complexes of organotellurium compounds as single source precursors.

Several intermetallic binary phases of Pd-Te including Pd3Te2, PdTe, PdTe2, Pd9Te4, Pd3Te, Pd2Te, Pd20Te7, Pd8Te3, Pd7Te2, Pd7Te3, Pd4Te and Pd17Te4 are known, and negligible work (except few studies on PdTe) has been done on exploring applications of such phases and their fabrication at nanoscale. Hence, Pd(ii) complexes Pd(L1)Cl2 and Pd(L2-H)Cl (L1): Ph-Te-CH2-CH2-NH2 and L2: HO-2-C6H4-CH[double bond, length as m-dash]N-CH2CH2-Te-Ph were synthesized. Under similar thermolytic conditions, complex Pd(L1)Cl2 with bidentate coordination mode of ligand provided nanostructures of Pd9Te4 (telluropalladinite) whereas Pd(L2-H)Cl with tridentate coordination mode of ligand yielded PdTe (kotulskite). Bimetallic alloy nanostructures possess high catalytic potential for Suzuki coupling of aryl chlorides, and reduction of 4-nitrophenol. They are also recyclable upto six reaction cycles in Suzuki coupling.

Organochalcogen ligands in catalysis of oxidation of alcohols and transfer hydrogenation.

Organochalcogen compounds have been used as the building blocks for the development of a variety of catalysts that have been studied comprehensively during the last two decades for several chemical transformations. Transfer hydrogenation (reduction of carbonyl compounds to alcohols) and oxidation of alcohols (conversion of alcohols to their respective ketones and aldehydes) are also among such chemical transformations. Some compilations are available in the literature on the development of catalysts, based on organochalcogen ligands, and their applications in Heck reaction, Suzuki reaction, and other related aspects. Some review articles have also been published on different aspects of oxidation of alcohols and transfer hydrogenation. However, no such article is available in the literature on the syntheses and use of organochalcogen ligated catalysts for these two reactions. In this perspective, a survey of developments pertaining to the synthetic aspects of such organochalcogen (S/Se/Te) based catalysts for the two reactions has been made. In addition to covering the syntheses of chalcogen ligands, their metal complexes and nanoparticles (NPs), emphasis has also been placed on the efficient conversion of different substrates during catalytic reactions, diversity in catalytic potential and mechanistic aspects of catalysis. It also includes the analysis of comparison (in terms of efficiency) between this unique class of catalysts and efficient catalysts without a chalcogen donor. The future scope of this area has also been highlighted.

Ultra-small palladium nano-particles synthesized using bulky S/Se and N donor ligands as a stabilizer: application as catalysts for Suzuki-Miyaura coupling.

Two chalcogenated ligands L1 and L2 containing anthracene core and amine functionality have been synthesized. Both the ligands have been characterized using 1H and 13C{1H} NMR techniques. The structure of L1 has also been corroborated by single crystal X-ray diffraction. Application of L1 and L2 as stabilizers for palladium nano-particles (NPs) has been explored and six different types of NPs 1-6 have been prepared by varying the quantity of stabilizer. The nano-particles have been characterized by PXRD, EDX, and HRTEM techniques. The size of NPs has been found to be in the range of ∼1-2 nm, 2-3 nm, 4-6 nm, 1-2 nm, 1-2 nm and 3-5 nm for 1-6 respectively. The catalytic activities of 1-6 have been explored for Suzuki-Miyaura coupling of phenyl boronic acid with various aryl halides. These NPs showed good catalytic activity for various aryl chlorides/bromides at low catalyst loading (5 mg). Among 1-6, the highest activity has been observed for NPs 1, probably due to their relatively small size and high uniformity in the dispersion. The recyclability of the NPs upto 5 catalytic cycles is a distinct advantage.