Category: 224311-51-7

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Neutral diphenylcarbenerhodium(I) complexes of the general composition trans-[RhX(=CPh2)(PiPr3)2] (X = F (3), OCN (4), CF3CO2 (5), PhCO2 (6), CF3SO3 (7)) were prepared from the chloro or bromo precursors trans-[RhCl(=CPh2)(PiPr3)2](1) and trans-[RhBr(=CPh2)(PiPr3)2] (2) by salt metathesis in acetone and isolated in excellent yields. While treatment of 1 with Tl(acac[F6]) afforded the substitution product trans-[Rh(kappa1-acac[F6])(=CPh2)(P iPr3)2] (8), the corresponding reaction of 1 with Tl(acac) gave the chelate compound [Rh(kappa2-acac)(=CPh2)(PiPr3)] (9) with only one phosphine ligand attached to the metal center. In acetone solution, the triflato complex 7 is in equilibrium with the cation trans-[Rh{O=C(CH3)2}(=CPh2)(P iPr3)2]+ which after addition of NaBAr4F precipitates as the BAr4F salt 11. The starting material 1 as well as the bis(triphenylphosphine) and bis(triisopropylstibine) analogues 14 and 15 react with pyridine or acetonitrile in the presence of KPF6 to yield the cationic complexes trans-[Rh(py)(=CPh2)(PPh3)2]PF6 (16) and trans-[Rh(CH3CN)(=CPh2)(L)2]PF6 (L = PiPr3 (17), SbiPr3 (18)). The BAr4F salt of the cation trans-[Rh(CH3CN)(=CPh2)(SbiPr3) 2]+ (19) was characterized by X-ray crystallography. Compounds 11, 16-19 and the bis(pyridine) derivative cis-[Rh(=CPh2)(NC5H5)2(P iPr3)]PF6 (12) are the first representatives of four-coordinate cationic diphenylcarbenerhodium(I) 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

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 Article，once mentioned of 224311-51-7, category: chiral-phosphine-ligands

Stereocontrolled Csp3 cross-coupling can fundamentally change the types of chemical structures that can be mined for molecular functions. Although considerable progress in achieving the targeted chemical reactivity has been made, controlling stereochemistry in Csp3 cross-coupling remains challenging. Here we report that ligand-based axial shielding of Pd(II) complexes enables Suzuki-Miyaura cross-coupling of unactivated Csp3 boronic acids with perfect stereoretention. This approach leverages key differences in spatial orientation between competing pathways for stereoretentive and stereoinvertive transmetalation of Csp3 boronic acids to Pd(II). We show that axial shielding enables perfectly stereoretentive cross-coupling with a range of unactivated secondary Csp3 boronic acids, as well as the stereocontrolled synthesis of xylarinic acid B and all of its Csp3 stereoisomers. We expect these ligand design principles will broadly enable the continued search for practical and effective methods for stereospecific Csp3 cross-coupling.

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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

Electric Literature of 224311-51-7, Chemistry can be defined as the study of matter and the changes it undergoes. You’ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl, molecular formula is C20H27P. In a patent, introducing its new discovery.

Herein, we have revealed elemental sulfur-and iodine reagent-mediated indole C3 arylations using cyclohexanones as the arylating reagent. This protocol provides an efficient gram-scalable access to 3-Arylindole and benzo[4,5]thieno[2,3-b]indole motifs with a broad range of compatible functionalities.

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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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl, molecular formula is C20H27P. In a Review，once mentioned of 224311-51-7, Quality Control of: 2-(Di-tert-Butylphosphino)biphenyl

Metalloenzymes play critical roles in the environment by catalyzing redox reactions in biogeochemical cycles. The elucidation of structure-function relationships in these biocatalysts has provided a foundation for the development of bioinspired catalysts for fuel production and small-molecule activation. In this Perspective, we highlight developments in engineered biomolecular and bioinspired catalysts for the reduction of H+, O2, and CO2 and for the oxidation of H2 and H2O. The roles of proton transfers and second-sphere interactions in particular are highlighted.

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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

Reference of 224311-51-7, An article , which mentions 224311-51-7, molecular formula is C20H27P. The compound – 2-(Di-tert-Butylphosphino)biphenyl played an important role in people’s production and life.

The Nozaki Ir-based CO2 hydrogenation catalyst was successfully immobilized on post-functionalized silica beads (d=200 mum) through click chemistry. This material hydrogenates CO2 into formic acid with turnover numbers reaching 2.8×104 in a batch reactor within 24 hours, paving the way towards the design of efficient heterogeneous catalysts for this transformation.

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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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl, molecular formula is C20H27P. In a Article，once mentioned of 224311-51-7, Formula: C20H27P

An extensive survey of the occurrences and origins of both structural trans-effects (STEs) and kinetic trans-effects (KTEs) in octahedral d-transition metal complexes is presented. This allows the identification of general STE classes into which the majority of common ligands fit: (a) very large STE ligands (STE vs. Cl- > ca. 0.20 A): SiR3-, NO-, N3-, O2-, S2-, RC3-; (b) large STE ligands (ca. 0.20 > STE vs. Cl- > ca. 0.10 A): H-, R-, eta1-alkenyl, eta1-Ph, RCO-, RN2-; (c) moderate STE ligands (ca. 0.10 A > STE vs. Cl- > 0.00 A): CO, CN-, CNR, eta1-acetylide, R2C, NO2-, NS+, RN2+, SO32-, RSO2-, PR3, P(OR)3, RNH-, RS-, eta1-thiones. The NO+ ligand best illustrates the mutual nature of STEs, since it shows moderate STEs when trans to pi-acceptor ligands, negligible STEs when trans to purely sigma-donor ligands, and inverse STEs when trans to pi-donors. STEs can sometimes show a marked dependency upon the electronic properties of the complexed metal centre, e.g. pi-accepting RNC and PR3 ligands generally give moderate STEs, but in d0 complexes their STEs are weaker than that of Cl-. This may be attributed to an absence of pi-back-bonding in such complexes. Also, the STEs of pi-donating RN2- ligands show an extremely wide variation which partially correlates with the metal d-configuration. The relationship between STEs and KTEs depends upon ligand substitution mechanisms, and because such reactions in octahedral complexes are generally dissociatively activated, there is often a close correlation between STEs and KTEs. For example, N3- causes very large STEs and KTEs, whilst SO32- gives moderate STEs and large KTEs. Since both of these ligands cause STEs primarily via powerful electron donation, the ground state destabilisations implied by STEs are likely to be accompanied by stabilisation of the electron-deficient five-co-ordinate transition states. By contrast, pi-acceptor ligands such as CO or RNC generally exert moderate STEs, but cause pronounced delabilisation of trans metal-ligand bonds due to destabilisation of transition states.

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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

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 Conference Paper，once mentioned of 224311-51-7, Recommanded Product: 224311-51-7

[FeFe]-hydrogenases are the most efficient biological catalysts available for the H2 evolution reaction. Their active site-the H-cluster-features a diiron subsite which has the peculiar characteristic of bearing cyanide groups hydrogen-bonded to the apoprotein as well as carbonyl ligands. Notably, one of the CO ligands is disposed in bridging position between the metal centers. This allows one of the Fe ions to retain a square pyramidal coordination-which determines the assumption of the so-called “rotated structure”-with a vacant coordination site in trans to the mu-CO group, ready to bind protons when the active site is in the FeIFeI state. Many FeIFeI biomimetic models have been synthesized and characterized so far, but most of them fail to reproduce the orientation of the diatomic ligands that is observed in the enzyme active site. In the present contribution we carried out a density functional theory investigation, with the aim of evaluating whether the establishment of hydrogen bonding at the level of cyanides is sufficient to favor rotation of ligands around one of the Fe centers, in analogy with the reduced H-cluster. To this end, we carried out an investigation of the potential energy surface of an isolated Fe2S2 model bearing CN and CO groups, as well as of the supramolecular complex formed by the diiron model and a porphyrin derivative hydrogen-bonded to the former. As far as the isolated Fe2S2 species are concerned, the sole mu-CO models individuated in the course of our potential energy surface scans are the ones in which both cyanides are bound to same iron center, while no CO-bridged minima could be found in the case of models having one CN group bound to each of the metal ions. The latter represents a major difference with respect to the coordination geometry of the reduced diiron subcluster in the enzyme. However, perturbation of the diiron model by a porphyrin ring designed to donate hydrogen bonds to the cyanide groups-thus, at least partially, reproducing the network of H-bond between the H-cluster and the apoprotein in [FeFe]-hydrogenases-significantly changes the picture in this regard. Therefore, possible strategies to modulate the disposition of ligands around the metal centers of biomimetic [FeFe]-hydrogenases models are discussed in light of computed geometries and relative stabilities of the supramolecular 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

Related Products of 224311-51-7. Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl

The reaction of bis(diphenylphosphino)acetylene(DPPA) with Co2(CO)8 in toluene at 80 C for 24 h resulted in an alkyne-bridged, diphosphine-chelated tetracobalt-complex, [Co2(CO)5{mu-P,P- (mu-PPh2C?CPPh2)}] [Co2(CO)4{mu-P- (mu-PPh2C?CPPh2)}] 3. The X-ray structural studies of 3 reveals that it can be regarded as a dimerized form of two DPPA bridged dicobalt complex, [Co2(CO)6 (mu-PPh2C?CPPh2)] 1.

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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

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 Article，once mentioned of 224311-51-7, Application In Synthesis of 2-(Di-tert-Butylphosphino)biphenyl

An auto-tandem Pd-catalyzed process consisting of an intramolecular direct arylation and an intermolecular Buchwald-Hartwig reaction for C-ring amino-substituted 1-methyl-1H-alpha-carboline synthesis has been developed. A mechanistic study of the direct arylation reaction revealed a rate effect of the inorganic base on the C-H activation step (“base effect”). The amines, reagents in the tandem protocol, appear to have a similar effect on the direct arylation.

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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

224311-51-7, Name is 2-(Di-tert-Butylphosphino)biphenyl, molecular formula is C20H27P, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 224311-51-7, name: 2-(Di-tert-Butylphosphino)biphenyl

Driven by population and quality of living increases, the global consumption of energy is expected to dramatically increase over the course of the century. To avoid meeting this demand with fossil fuels, new carbon neutral energy sources must be implemented which are competitive in cost and performance with those currently in use. Hydrogen is a possible candidate to meet this need but carbon-free production of hydrogen needs to be developed. This chapter specifically examines the progress of homogeneous catalysts used in hydrogen production via artificial photosynthesis. Only those catalysts based on earth abundant metals, such as Co, Ni, Fe, and Mo are discussed as inexpensive mass production would require such materials, as opposed to expensive and rare metals, such as Pt, Pd and Rh. Electrocatalytic studies are also discussed as it pertains to the light driven systems and mechanistic insights.

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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