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Hydride transfer between transition metal hydride complexes and carbon dioxide is a known reaction, where the thermodynamically favored direction of hydride transfer determines whether CO2 reduction or formate oxidation occurs. Analysis of a growing database of thermodynamic parameters for transition metal hydride complexes now provides clear demarcation between metal hydrides which will function as oxidases and as reductases. The turning point is set at the hydricity of formate (44 kcal/mol in acetonitrile). Here, we utilize hydricity as a framework to reevaluate the catalytic activity and proposed mechanisms for formate oxidation and CO2 reduction with several Ni and Rh P2N2 (P2N2 = 1,5-diaza-3,7-diphosphacyclooctane) complexes, respectively. The series of Ni P2N2 complexes have hydricities between 55-64 kcal/mol and are active catalysts for the electrochemical oxidation of formate. A surprising correlation of increased rate of electrochemical oxidation with decreased overpotential, nu, is observed. The Rh P2N2 complexes have hydricities between 28-34 kcal/mol and function as hydrogenation catalysts for the reduction of CO2 to formate. Learning from the reactivity of these catalysts, design principles for future metal hydride complexes are presented that focus on the ultimate goal of catalyst optimization for improved energy efficiency (overpotential) with high selectivity (Faradaic efficiency) for both formate oxidation and CO2 reduction to formate.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The mechanism of Pd-catalyzed, Friedel-Crafts intermolecular acylation of arenes to ketones was comprehensively investigated by using DFT calculations. The calculated results revealed that this transformation was composed of several key steps: C-I bond oxidative addition, CO insertion, reductive elimination and C-H bond functionalization. Of these steps, the last was found to be the rate-determining step, and it occurred much more easily with strongly electrophilic aroyl triflate compared to other resultant counterparts. In addition, our calculation provides a rationale for experimental findings that simple Pd salts exhibit superior catalytic abilities compared to phosphine-ligated Pd catalysts.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A new benzo[c]carbazolyl-based phosphine ligand has been designed and synthesized. This newly developed ligand efficiently facilitates the Pd-catalyzed tetra-ortho-substituted biaryl syntheses via Suzuki-Miyaura cross-coupling. With 1 mol% of the Pd(OAc)2/L6 catalyst, sterically congested biaryls were afforded in good-to-excellent yields. In particular, the mild reaction conditions exhibited good compatibility of heterocycles and functional groups including esters and nitrile. L6 was structurally characterized by X-ray crystallographic analysis.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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One-pot synthesis of (nitronyl nitroxide)-gold(i)-phosphine (NN-Au-P) complexes has been developed using chloro(tetrahydrothiophene)gold(i), phosphine ligands, nitronyl nitroxide radicals, and sodium hydroxide. The NN-Au-P complexes can be easily handled because they were quite stable under aerated conditions in both solution and crystalline states. They showed weak absorption bands with vibrational structures in the 450-650 nm region. The oxidation potentials assigned to the NN moieties of NN-Au-P complexes with aromatic phosphines were observed around ?0.1 V vs. Fc/Fc+ (?0.11 V for NN-Au-1, ?0.08 V for NN-Au-2, ?0.13 V for NN-Au-5, and ?0.07 V for NN-Au-6), somewhat lower than that of NN-Au-P complexes with aliphatic phosphines (?0.25 V for NN-Au-3 and ?0.17 V for NN-Au-4).

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A contemporary undergraduate laboratory experiment incorporating parallel microscale experimentation was developed for the well-defined palladium catalyzed Suzuki-Miyaura cross coupling of 4-fluorophenylboronic acid with both 4-chloro- and 4-bromoanisole using 11 diverse phosphine ligands and one ligandless control. This laboratory introduces students to low-barrier high-throughput experimentation (HTE) technique that is widely utilized in both academic and industrial research settings. This experiment compliments current topics discussed in organic chemistry, inorganic chemistry, and organometallic chemistry lecture courses and serves to reinforce the students’ understanding of fundamental concepts of transition metal mediated cross-coupling reactions. Students are also exposed to common analytical tools (thin layer chromatography (TLC) and high-pressure liquid chromatography (HPLC)) used in research settings to analyze the corresponding experimental data.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Agold-catalyzed phenol synthesis was successfully used in the synthesis of dihydroisocoumarins for the first time.Alarge number of gold(I) complexes were prepared and tested; only complexes based on the biarylphosphine motif were successful. CSIRO 2014.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Three dinuclear gold(i) p-arylene(diethynyl) complexes with the same peripheral isocyanide ligation and different central conjugated moieties have been prepared and their supramolecular polymerization was comprehensively studied. The central, core-forming pi-conjugated arylene moieties present in the complexes have been shown to exhibit a pronounced influence on the resulting photophysical properties, self-assembly mechanisms, morphologies and gelation behavior of the supramolecular polymers. Complexes 1 and 2 bearing biphenylene and phenylene central chromophores exhibit a cooperative mechanism during the supramolecular polymerization, with the appearance of pronounced low-energy phosphorescence attributed to the aurophilic interactions. In contrast, compound 3 with a central benzothiadiazole moiety was found to undergo self-assembly via an isodesmic mechanism. Due to the presence of stronger pi-pi interactions, complexes 1 and 3 possess lower DeltaG0 values for self-assembly and a stronger tendency to form metallogels. Given the balance between the non-covalent interaction enthalpy of the core-forming moieties and intercoronal chain repulsion, 1 and 3 tend to form one-dimensional fibers, while 2 with a short central chromophore is likely to form zero-dimensional spherical aggregates.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Early and late transition metal-carbon multiple bonds that have been widely used for many catalytic processes, organic transformations, and olefin metathesis reactions are described. Especially, the development of Schrock and Fischer type olefin metathesis catalysts aided by computational studies is discussed, focusing on work that aims at improving the reactivity, stability, and regioselectivity. The intriguing electronic feature and reactivity of a titanium alkylidyne, which leads to many unique transformations of organic molecules, are summarized. The development of Fischer type olefin metathesis catalysts to control the regioselectivity in cyclopolymerization of diynes with RuII-alkylidene catalysts employing quantum chemical studies is summarized.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Structural features of 26 mononuclear octahedral monooxo d2-Re(V) complexes with singly charged oxygen atoms of bidentate-chelating (O,N) ligands (Ln), namely, [ReO(Ln)(Lmono)3] (where Lmono stands for a monodentate ligand) containing six- and seven-membered chelate rings ReNC3O and ReNC4O, are considered. The atoms O(Ln), with one exception, are in the trans positions to ligands O(oxo). In [ReO(OPPh3)Cl2(L35)], the trans position to the oxo ligand is occupied by the neutral oxygen atom of ligand OPPh3. In [ReO(Hal)2(Ln)(Lmono)] [(Lmono = PPh3, AsPPh3, and OPPh3)] structures, two geometric isomers exist: halide ligands are either in the cis- or in the trans position to each other.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The utilization of CO2 as a C1 building block for the synthesis of valuable chemicals is of great importance. The transition metal-catalyzed carboxylation of unsaturated substrates with CO2 has proved to be an effective and versatile strategy for the incorporation of CO2 in organic substrates with unsaturated bonds. Different kinds of carboxylation reactions with CO2 have provided a direct access to a myriad of functionalized carboxylic acids and derivatives. This review focuses on carboxylation of unsaturated substrates with CO2 via transition metal catalysis. Various kinds of carboxylations with different catalytic systems are discussed.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate