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In the present study, we use computational quantum chemistry to examine the nickel-catalyzed three-component coupling for transforming CO2 into a homoallylic alcohol. We find that the reaction is limited by several Ni-assisted atom transfer reactions in the catalytic cycle, in which a new product formation pathway is found from our calculations. Our results also point towards several key factors for an efficient reaction. Thus, substrates that would lead to a stabilized alkene facilitate a key step in the catalytic cycle. The optimal phosphine ligand should provide a good balance between directing stereochemistry with its steric bulk and enabling the reaction without being excessively bulky. Our calculations also highlight the importance of carefully chosen substrates and ligands in order to avoid potential side reactions, and that knowing the conformational preference in the substrate alone may not be sufficient for predicting the stereochemistry.

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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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Using density functional theory calculations (at the B97-D2//BP86 level) and measurements of kinetic isotope effects, we explored the mechanism of [RuH2(PPh3)3(CO)] (22) in catalytic acceptor-less dehydrogenation of methanol to formaldehyde. 22 is found to exhibit a similar activity as the previously studied [RuH2(H2)(PPh3)3] (1 b) complex. On the computed pathway, eta2?eta1 slippage of Ru-bound formaldehyde prior to decoordination is indicated to be rate-limiting, consistent with the low kH/kD KIE of 1.3 measured for this reaction. We also explored computationally the possibility of achieving complete dehydrogenation of methanol (into CO2 and H2), through subsequent decarbonylation of formaldehyde and water-gas shift reaction of the resulting carbonyl complex. Complete pathways of this kind are traced for 22 and for [RuH2(PPh3)2(CO)2]. An alternative mechanism, involving a gem-diol intermediate (obtained upon attack of OH? to coordinated formaldehyde), has also been investigated. All these pathways turned out to be unfavourable kinetically, in keeping with the lack of CO2 evolution experimentally observed in this system. Our calculations show that the reactions are hampered by the low electrophilicities of the CO and HCHO ligands, making OH? uptake unfavourable. Consequently, the subsequent intermediates are too high-lying on the reaction profiles, thus leading to high kinetic barriers and preventing full dehydrogenation of methanol to occur by this kind of mechanism.

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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 discovery, in the mid 1990s, that certain cobalt, ruthenium and copper complexes could effectively control the radical polymerization of a number of polar olefins, allowing for the facile synthesis of complex macromolecular architectures, fostered an intense search for increasingly better performing catalysts. As a consequence, several metal complexes were designed and tested. This article presents an organized and detailed overview of the most significant developments in the use of transition metal compounds to initiate, mediate and control radical polymerization, i.e., atom transfer radical polymerization or organometallic mediated radical polymerization. The catalysts have been classified according to the group of the periodic table to which the relative metal centers belong. Their catalytic performance, the mechanism with which they are supposed to operate, the structure-reactivity correlations as well as the type of monomers and experimental conditions employed are described. The use and the role of non-transition metal complexes in controlled radical polymerization are also 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

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A series of bis-orthometalated monocyano Ir(III) complexes, [Ir(ppy)2PX3CN], (X=Oph, Ph and n-bu) were synthesized and the influence of the steric and electronic effects of the phosphine ligand on the photophysical and electrochemical properties of complexes were studied. These cyano phosphine complexes emit light from an admixture of triplet metal-to-ligand charge-transfer (3MLCT) and ligand centered (LC) states in the region of 455-498 nm with a vibronic progression. The trends of the photophysical and electrochemical properties of metal complexes in the series were well understood by the electronic parameter of the phosphine ligands. Polymer light emitting devices were fabricated by doping Ir(ppy)2P (n-bu)3CN in the PVK host and the device performances were investigated. The maximum external quantum efficiency (etaex) was 1.45% for a 10 wt% Ir(ppy)2P(n-bu)3CN doped PVK device. A power efficien cy of 0.99 lm/W at 230 cd/m2 and 6 mA/cm2 was obtained. The corresponding chloro complexes of the general formula [Ir(ppy)2PX3Cl] were also synthesized and the optical and device properties were compared with the cyano complexes.

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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 reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl, molecular formula is C20H27P. In a Chapter,once mentioned of 224311-51-7, Recommanded Product: 224311-51-7

Arguably, one of the biggest advancements in synthetic chemistry over recent decades, has been the development of Pd cross-coupling procedures. The application of Pd-catalyzed cross-coupling reactions is nowadays a powerful and widely applied tool during the preparation of a wide range of pharmaceuticals, agrochemicals, and synthetic intermediates. Recently, the use of cheaper, more abundant, and less toxic first-row transition metals to replace more expensive Pd has started to attract significant attention. While at the same time, direct C?H functionalization to replace the necessity of halogenated precursors is also a topic of interest in order to develop cleaner and more environmentally friendly procedures. In this context, cobalt-catalyzed C?H functionalization has provided a platform to address these desires. The mechanistic diversity of newly developed protocols using cobalt is quite extraordinary and more varied than when applying the corresponding second and third row analogs. This overview seeks to exemplify and highlight the potential of cobalt as the basis for C?H functionalization protocols, focusing on the wide range of mechanisms available arising from the rich redox chemistry of this metal.

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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 reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl, molecular formula is C20H27P. In a Review,once mentioned of 224311-51-7, SDS of cas: 224311-51-7

A detailed overview on the synthesis of four-, five- and six-membered, saturated and unsaturated N-heterocyclic carbenes used in the preparation of their corresponding ruthenium complexes (Grubbs’ second-generation, Fischer-type, Hoveyda-Grubbs, homo and hetero-bimetallic) is presented both in solution and on solid support. The catalytic activity of the different complexes in ruthenium-catalyzed metathesis reaction is compared and explained by their structural features.

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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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Noble-metal-free systems with bio-inspired diiron dithiolate mimics of the [FeFe]-hydrogenase active site, namely, [(mu-pdt)Fe2(CO) 5L] [pdt=propanedithiolate; L=P(CH2OH)3 (1), P(CH3)3 (2)], as water reduction catalysts with xanthene dyes as photosensitizers and triethylamine as a sacrificial electron donor were studied for visible-light-driven water reduction to hydrogen. These systems display good catalytic activities with the efficiencies in hydrogen evolution of up to 226 turnovers for 1, if Eosin Y was used as the photosensitizer in an environmentally benign solvent (EtOH/H2O) after 15 h of irradiation (I?”>450 nm) under optimal conditions. Under all of the conditions adopted, 1 that has a water soluble phosphine ligand, P(CH2OH) 3 displayed a higher efficiency than 2, which bears a PMe3 ligand. The photoinduced electron transfer in the systems was studied using fluorescence, transient absorption, time-resolved UV/Vis, and in situ electron paramagnetic resonance (EPR) spectroscopy. A new electron-transfer mechanism is proposed for hydrogen evolution by these iron-based photocatalytic systems.

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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

Discovery of 2-(Di-tert-Butylphosphino)biphenyl

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Metal nanoparticle-catalyzed reactions such as hydrogenation, cross-coupling, carbonylation, and hydroformylation reactions are the most widely used reactions in the pharmaceutical and fine chemical industries. However, there is no operando spectroscopic technique that exists to monitor the size of functioning nanocatalyst. By exploiting localized surface plasmon resonance of catalytically relevant nanostructures, such as monometallic (e.g., Pd, Pt, Ni, Rh, Au, and Cu) nanoparticles and bimetallic core?shell (e.g., Ag-Pd) nanoparticles, we show UV?Vis spectroscopy can be used to determine the size of functioning nanocatalyst. Based on our finite-difference time-domain simulations, it is possible to detect leaching of even a monolayer of atoms from the surface of widely used metal nanocatalysts with a conventional UV?Vis spectrometer. This sensitive, inexpensive and robust spectroscopic approach can be potentially used as in-line process analytical technology (PAT) in pharmaceutical development and manufacturing.

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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

Discovery of 2-(Di-tert-Butylphosphino)biphenyl

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BN/CC isosterism has emerged as a viable strategy to expand the chemical space of organic molecules. In particular, the application of BN/CC isosterism to arenes has received significant attention due to the vast available chemical space provided by aromatic hydrocarbons. The synthetic efforts directed at assembling novel aromatic BN heterocycles have resulted in the discovery of new properties and functions in a variety of fields including biomedical research, medicinal chemistry, materials science, catalysis, and organic synthesis. This tutorial review specifically covers recent advances in synthetic technologies that functionalize assembled boron-nitrogen (BN) heterocycles and highlights their distinct reactivity and selectivity in comparison to their carbonaceous counterparts. It is intended to serve as a state-of-the-art compendium for readers who are interested in the reaction chemistry of BN heterocycles.

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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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Ligands are essential for controlling the reactivity and selectivity of reactions catalysed by transition metals. Access to large phosphine ligand libraries has become an essential tool for the application of metal-catalysed reactions industrially, but these existing libraries are not well suited to new catalytic methods based on non-precious metals (for example, Ni, Cu and Fe). The development of the requisite nitrogen-and oxygen-based ligand libraries lags far behind that of the phosphines and the development of new libraries is anticipated to be time consuming. Here we show that this process can be dramatically accelerated by mining for new ligands in a typical pharmaceutical compound library that is rich in heterocycles. Using this approach, we were able to screen a structurally diverse set of compounds with minimal synthetic effort and identify several new ligand classes for nickel-catalysed cross-electrophile coupling. These new ligands gave improved yields for challenging cross-couplings of pharmaceutically relevant substrates compared with those of those of previously published ligands.

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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