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Mesoporous Materials in Heterogeneous Catalysis
Published in Varun Rawat, Anirban Das, Chandra Mohan Srivastava, Heterogeneous Catalysis in Organic Transformations, 2022
Meenal Batra, Ashutosh Sharan Singh
Oxidation of unsaturated hydrocarbons, like cyclohexene, has been shown through Cu-based MOF [68] [Cu(H2btec)(bipy)]∞ by Spodine and co-workers. Mixed ligand of 2,2′-bipyridine and 1,2,4,5-benzenetetracarboxylic acid was used for MOF synthesis through hydrothermal technique. In the single-crystal structure, Cu(II) centre has distorted square planar geometry. With tert-butyl hydroperoxide (TBHP), cyclohexene can be transformed into a mixture of the corresponding epoxide and 2-cyclohexenone, respectively. The reported MOF [Cu(H2btec)(bipy)]∞, shows a high value for the conversion of cyclohexene (64.5%) at 75 °C for 24 h. The mechanism was proposed on the basis of literature report [69–71]. In the first step, distal O-atom of TBHP interacts with Cu(II) centre with an extension of the coordination number. Meanwhile, nucleophilic attack of cyclohexene on the coordinated O-atom of TBHP followed by concerted O-transfer leads to the formation of coordinated epoxide at the Cu-centre. With the subsequent elimination of epoxide, the catalyst was regenerated for the next round.
The Tertiary Organometallic Reagent Promoted Reductive Coupling of Aryl Halides
Published in John R. Kosak, Thomas A. Johnson, Catalysis of Organic Reactions, 2020
Caubere has reported the dimerization of aryl chlorides utilizing the complex reducing agent [13] formed from sodium hydride, tert-amyl alcohol, nickel salts, and a ligand in THF. Caubere found that the use of triphenylphosphine as the sole ligand led to the formation of phenyl-substituted products from the decomposition reactions of zero valent nickel complexes in addition to substantial amounts of reduction products. Substitution of 2,2′-bipyridine for the triphenylphosphine ligand virtually eliminated the products form the phenyl transfer reaction and reduced reduction products to less than one-half of the value observed with the phosphine ligand. Following the Caubere example, the reaction was repeated with only 2,2′-bipyridine present as ligand. The resultant product mixture contained almost exclusively the reduction product with only a trace of biaryls present. Repetition of our work with the addition of 2 equivalents of 2,2′-bipyridine per equivalent of nickel in addition to the 2 equivalents of triphenylphosphine gave very positive results as the yield of biaryl products increased to about 70%. This new approach to the dimerization of aryl chlorides has not been investigated and this report partially details the findings in our investigations [14].
Polymers
Published in Bryan Ellis, Ray Smith, Polymers, 2008
Processing & Manufacturing Routes: Prod. by polymerisation of 2,5-dichlorobenzophenone with Ni(0), (generated in situ from NiCl2 and Zn) and triphenylphosphine in a suitable solvent such as dimethylformamide or dimethylacetamide [4,8,9,10,11]. The addition of 2,2 -bipyridine as a co-ligand in preparation results in formation of polymer with different physical and optical properties [1,2,4].
Preparation, characterization, and photoluminescent and semiconductive properties of an iron compound
Published in Inorganic and Nano-Metal Chemistry, 2022
Qiuyan Luo, Yang-Qing Chen, Hai-Qi Peng, Qiong Ji, Xuan-Xuan Wang, Lijun Wei, Qiu-Yue Zhong, Wen-Tong Chen
Supramolecular chemistry has recently attracted more and more attention to prepare new solid compounds, because it has advantage of self-assembly to synthesize compounds by means of weak cooperative interactions like hydrogen bondings, π-π stacking and dipole-dipole interactions to interlink building blocks together and large numbers of supramolecular compounds have so far been documented.[1,2] Metal bipyridine compounds have nowadays obtained increasing interest, because of their intrinsic esthetic appeals and attractive properties such as electrochemical sensors,[3] catalysts,[4] redox mediators[5] and so on; these properties endow metal bipyridine compounds with many potential applications in luminescence materials,[6] catalysts,[7] electrochemical cells,[8] etc. The pyridyl rings of the bipyridine are characterized by a delocalized π-electron system. Bipyridine is therefore a useful ligand for synthesizing light emitting materials which are able to be used in many areas like chemical sensors, organic light emitting diodes and solar energy conversion. Moreover, bipyridine is a bifunctional ligand and it is able to act as a bidentate ligand to coordinate to several metal ions.
Photoluminescence, semiconductive properties and TDDFT calculation of a novel cadmium bipyridine complex
Published in Inorganic and Nano-Metal Chemistry, 2020
To our knowledge, complexes containing group 12 elements are attractive due to their optical and photoluminescence properties, their wide applications, the important role of zinc played in biological systems, and the rich coordination geometry afforded by the d10 electronic configuration of the group 12 ions.[1,2] Meanwhile, the 4,4′-bipyridine (bipy) possesses a delocalized π-electron system on the pyridyl rings and it is a useful building unit in synthesizing a supramolecular or extended structure, because its nitrogen atoms endow it to bind to metal ions. Moreover, the bipy is a rod-like and rigid organic ligand for the preparation of complexes. For example, the bipy can act as a pillar to connect to an inorganic skeletal backbone, a charge-compensating ion, a bridge connecting two metal complex moieties, a ligand linking a metal to an inorganic framework, or an uncoordinated guest molecule.[3,4] As a result, the bipy has recently attracted more and more attention in preparing light emitting complexes that might have potential applications in many areas like organic light emitting diodes, chemical sensors, sensitizers in solar energy conversion, and so forth.[5,6] My recent efforts in preparing novel complexes containing group 12 elements have focused mainly on the synthesis of the bipy-containing complexes with photoluminescence or optical properties. I report herein the synthesis, X-ray crystal structure, photoluminescence, semiconductive properties and TDDFT calculation of a cadmium bipyridine complex, [Cd(bipy)3(H2O)2]n·2n(Et-Bipy)·n(bipy)·2nCl (1) (bipy = 4,4’-bipyridine, Et = ethyl group), which was prepared from a solvothermal reaction and is characteristic of a 1-D chain-like structure.
Noncovalent-bonded 2D–3D Zn2+, Cd2+, and Cu2+ supramolecular coordination complexes with 2,2′-bipyridine and carboxylates: their synthesis and characterization
Published in Journal of Coordination Chemistry, 2018
Jian-Ming Pan, Yin-Biao Ma, Jiong Shen, Bin Liu, Hui Liu, Shou-Wen Jin, Da-Qi Wang
For various coordination with metal ions and the ability to function as H-bond acceptors and donors, carboxylic acids have been explored in the design of coordination compounds [8, 9]. The chelating 2,2′-bipyridine has several appealing structural and chemical properties as rigidity, planarity, aromaticity, and basicity. This makes it a versatile ligand in synthesizing coordination compounds [10].