Awesome and Easy Science Experiments about (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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The alkoxycarbonylation of alpha-chloro ketones with carbon monoxide in alcoholic solvents could be optimized to generate beta-keto esters in high yields using much lower catalyst loadings than previously reported in the literature. Among the different screened parameters, the nature of the ligand proved to be the most crucial one, the Xantphos ligand affording the highest yields. The scope of the reaction could then be extended to a wide variety of chloro ketones with different types of alcohols. Copyright

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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

Extended knowledge of (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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Carboxylic acids and their derivatives are abundant and inexpensive organic and biomass-derived platform molecules, and their conversion into high-value products represents an important goal. Recently, visible-light photoredox decarboxylative coupling reactions have become an important chemical transformation because of their wide substrate scope, mild reaction conditions, high efficiency, and practicability. This review summarizes recent advances in visible-light photoredox decarboxylative coupling strategies, which include the formation of C?C and C?Y (Y=heteroatom) bonds.

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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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Reactions of the dinuclear palladium(I) complex, [Pd2(RNC)6](PF6)2 (R = 2,6-xylyl (Xyl), 2,4,6-mesityl (Mes)), with 1,1?-bis-(diphenylphosphino)ferrocene (dppf) gave dipalladium(I) complexes with dppf ligands, [Pd2(dppf)2(RNC)2](PF6)2 (1, R = Xyl, 66%; 2, R = Mes, 18%), which were characterized by elemental analysis, 1H- and 31P-NMR spectroscopy, IR and UV-vis absorption spectroscopic analyses, and cyclic voltammetry. The structure of 1 was characterized by X-ray crystallography. The cation of compound 1 is composed of two Pd(I) atoms joined by a Pd-Pd sigma-bond (2.602(1) A), and each palladium ion has a square planar structure ligated by a terminal isocyanide, two P atoms of dppf, and the neighboring Pd atom. The dppf ligands chelate to the metal with an average P-Pd-P bite angle of 99.19 and an average Pd…Fe distance of 4.236 A. The cyclopentadienyl rings of dppf ligands are in staggered form. The 1H- and 31P-NMR and the electronic absorption spectra of 1 and 2 indicated that the metal-metal bonded structure as observed in the crystal of 1 was retained in the solution. Complexes 1 and 2 were extremely photosensitive, and underwent a homolytic cleavage even under a room light. The reaction was monitored by the electronic absorption spectral changes and might generate a cation radical, [Pd(dppf)(RNC)]+. The cyclic voltammograms of 1 and 2 in acetonitrile solution showed two successive quasi-reversible oxidation waves at E1/2 = 0.60, 0.72 V (vs. Ag/AgPF6) (1) and 0.62, 0.73 V (2) and an irreversible reduction wave at E1/2 = -1.23 V (1) and -1.22 V (2). The former oxidation waves can be assigned to Fe(II)/Fe(III) processes of the two ferrocenyl groups and demonstrated that a charge-transfer communication between the Fe centers occurred through the Pd-Pd single bond.

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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 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. 12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, molecular formula is C34H28FeP2. In a Article,once mentioned of 12150-46-8, Application In Synthesis of 1,1-Bis(diphenylphosphino)ferrocene

Addition of ligands to [Pd(eta3-RCH-CH-CH2) (mu-Cl)]2 or chloride ions to cationic [(eta3 -RCH-CH-CH2)PdL2] +BF4 – induces the formation of neutral complexes eta1 -RCH-CH-CH2-PdClL 2 (R=H with L=(4-Cl-C6 H4) 3P, (4-CH3-C6H 4) 3P, (4-CF3-C6 H4) 3P or L2=1,2-bis(diphenylphosphino) butane (dppb), 1,1?-bis(diphenylphosphino)ferrocene (dppf); R=Ph with L=(4-Cl-C6H4)3P), instead of the expected cationic complexes [(eta3-RCH-CH- CH2) PdL2]+Cl-. In the presence of chloride ions, the reaction of morpholine with the cationic complexes [(eta 3-allyl)Pd (PAr3)2]+BF 4- (Ar=4-Cl-C6H4, 4-CH 3- C6H4) goes slower and involves both cationic [(eta3-allyl)Pd(PAr3)2] + and neutral eta1-allyl-PdCl(PAr3) 2 complexes as reactive species in equilibrium with Cl-. The cationic complex is more reactive than the neutral one. However, their relative contribution in the reaction strongly depends on the chloride concentration, which controls their relative concentration. The neutral eta1-allyl-PdCl(PAr3) 2 may become the major reactive species at high chloride concentration. Consequently, [Pd(eta3-allyl)(mu-Cl)] 2 associated with ligands or cationic [(eta3 -allyl) PdL2]+BF4-, used indifferently as precursors in palladium-catalyzed allylic substitutions, are not equivalent. In both situations, the mechanism of the Pd-catalyzed allylic substitution depends on the concentration of the chloride ions, delivered by the precursor or purposely added, that determines which species, [(eta3-allyl) PdL2]+ or/and eta1-allyl- PdClL2 are involved in the nucleophilic attack with consequences on the rate of the reaction and probably on its regioselectivity. Consequently, the chloride ions of the catalytic precursors [Pd(eta3-allyl)(mu-Cl)] 2 must not be considered as ‘innocent’ 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

Extended knowledge of (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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We report a catalyst for intermolecular hydroamination of vinylarenes that is substantially more active for this process than catalysts published previously. With this more reactive catalyst, we demonstrate that additions of amines to vinylarenes and dienes occur in the presence of potentially reactive functional groups, such as ketones with enolizable hydrogens, free alcohols, free carboxylic acids, free amides, nitriles, and esters. The catalyst for these reactions is generated from [Pd(eta3-allyl)CI]2 (with or without added AgOTf) or [Pd(CH3CN)4](BF 4)2 and Xantphos (9,9-dimethyl-4,5-bis(diphenylphosphino) xanthene), which generates complexes with large P-Pd-P bite angles. Studies on the rate of the C-N bond-forming step that occurs by attack of amine on an eta3-phenethyl and an eta3-allyl complex were conducted to determine the effect of the bite angle on the rate of this nucleophilic attack. Studies on model eta3-benzyl complexes containing various bisphosphines showed that the nucleophilic attack was faster for complexes containing larger P-Pd-P bite angles. Studies of substituted unsymmetrical and unsubstituted symmetrical model eta3-allyl complexes showed that nucleophilic attack on complexes ligated by Xantphos was faster than on complexes bearing ligands with smaller bite angles and that nucleophilic attack on unsymmetrical allyl complexes with larger bite angle ligands was faster than on unsymmetrical allyl complexes with smaller bite angle ligands. However, monitoring of catalytic reactions of dienes by 31P NMR spectroscopy showed that the concentration of active catalyst was the major factor that controlled rates for reactions of symmetrical dienes catalyzed by complexes of phosphines with smaller bite angles. The identity of the counterion also affected the rate of attack; reactions of allylpalladium complexes with chloride counterion occurred faster than reactions of allylpalladium complexes with triflate ortetrafluoroborate counterion. As is often observed, the dynamics of the allyl and benzyl complexes also depended on the identity of the counterion.

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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

Simple exploration of (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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The present invention relates to the field of catalysts for the polymerization of olefins, in particular, relates to the heteronuclear double-metal complex and its preparation method and prepare the bimodal distribution of the olefin polymer in the application. The heteronuclear double-metal complex of formula (1) shown in the complex. The invention of heteronuclear double-metal complex in the catalytic olefin polymerization will show high catalytic activity, can be used as the main catalyst polymerization, the adoption of the heteronuclear double-metal complex as the main catalyst can be in a single reactor under the use of a catalyst system to obtain the obvious on the bimodal distribution of the olefin polymer. (by machine translation)

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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

Awesome and Easy Science Experiments about 1,1-Bis(diphenylphosphino)ferrocene

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Experiments and density functional calculations were used to quantify the impact of the Pd-Ti interaction in the cationic heterobimetallic Cl2Ti(NtBuPPh2)2Pd(eta3-methallyl) catalyst 1 used for allylic aminations. The catalytic significance of the Pd-Ti interaction was evaluated computationally by examining the catalytic cycle for catalyst 1 with a conformation where the Pd-Ti interaction is intact versus one where the Pd-Ti interaction is severed. Studies were also performed on the relative reactivity of the cationic monometallic (CH2)2(NtBuPPh2)2Pd(eta3-methallyl) catalyst 2 where the Ti from catalyst 1 was replaced by an ethylene group. These computational and experimental studies revealed that the Pd-Ti interaction lowers the activation barrier for turnover-limiting amine reductive addition and accelerates catalysis up to 105. The Pd-Ti distance in 1 is the result of the NtBu groups enforcing a boat conformation that brings the two metals into close proximity, especially in the transition state. The turnover frequency of classic Pd pi allyl complexes was compared to that of 1 to determine the impact of P-Pd-P coordination angle and ligand electronic properties on catalysis. These experiments identified that cationic (PPh3)2Pd(eta3-CH2C(CH3)CH2) catalyst 3 performs similarly to 1 for allylic aminations with diethylamine. However, computations and experiment reveal that the apparent similarity in reactivity is due to very fast reaction kinetics. The higher reactivity of 1 versus 3 was confirmed in the reaction of methallyl chloride and 2,2,6,6-tetramethylpiperidine (TMP). Overall, experiments and calculations demonstrate that the Pd-Ti interaction induces and is responsible for significantly lower barriers and faster catalysis for allylic aminations.

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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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Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn’t involve a screen. 166330-10-5, C36H28OP2. A document type is Article, introducing its new discovery., Application In Synthesis of (Oxybis(2,1-phenylene))bis(diphenylphosphine)

In this paper, we report six phosphorescent Cu(I) complexes with 1,10-phenanthroline-derived ligands and phosphorous ligands, including their synthesis, crystal structures, photophysical properties, and electronic nature. The Cu(I) center has a distorted tetrahedral geometry within the Cu(I) complexes. Theoretical calculation reveals that all emissions originate from triplet metal-to-ligand-charge-transfer excited state. It is found that the introduction of alkyl moieties into 2,9-positions of 1,10-phenanthroline is highly effective on restricting the geometric relaxation that occurs in excited states, which greatly enhances the photoluminescence (PL) performances, including PL quantum yield improvement, PL decay lifetime increase, and emission blue shift.

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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

Some scientific research about 1,1-Bis(diphenylphosphino)ferrocene

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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. 12150-46-8, Name is 1,1-Bis(diphenylphosphino)ferrocene, molecular formula is C34H28FeP2. In a Article,once mentioned of 12150-46-8, Product Details of 12150-46-8

The rhenacarborane salt Cs[Re(CO)3(eta5-7,8-C2B9H 11)] (1) has been synthesized in excellent yield using a new procedure. Treatment of CH2Cl2 solutions of 1 with [RuCl2(PPh3)3] yields the exo-closo complex [Re(CO)3(eta52,3,10-(mu-H) 3-exo-{RuCl(PPh3)2}-7,8-C2B 9H8)] (2a). In this molecule a [RuCl(PPh3)12]+ moiety is exopolyhedrally bound via three B – H – Ru bonds to a closo-3,1,2-ReC2B9 system. An X-ray diffraction study revealed that one of these agostic interactions utilizes a beta-B-H bond in the coordinating CCBBB face of the cage, while the source of the remaining two B – H – Ru bonds is in the 65 belt. The anion of salt 1 also binds exopolyhedral [Rh(PPh3)2]+ and [Rh{Fe(eta-C5H4PPh2)2}] + fragments in the complexes [Re-(CO)3(eta5-5,10-(mu-H)2-exo-(RhL 2)-7,8-C2B9H9)] (L2 = (PPh3)2 (3a), {Fe(eta-C5H4PPh2)2} (3b)). Reaction of 1 with the salts [M(CO)2(THF)(eta-C5H5)] [BF4] (M = Fe, Ru) and [Fe(CO)2(THF)-(eta-C5Me5)][BF4] gives the complexes [Re(CO)3(eta5-n-(muH)-exo-{M(CO) 2(eta-C5R5)}-7,8-C2B 9H10)] (M = Fe, R = H, n = 10 (4a); M = Ru, R = H, n = 10 (4b); M = Fe, R = Me, n = 10 (4c), 9 (4d)) with isomers 4c and 4d formed as an inseparable mixture. An X-ray structural study on 4b revealed that there was no Re-Ru bond and that an exro-[Ru(CO)2(eta-C5H5)]+ fragment is bound to the rhenacarboranyl anion by a single unsupported B – H – Ru interaction with an unusually long B – Ru distance (2.695(13) A). The compounds [ReM(mu-10-H-eta5-7,8-C2B9H 10)-(CO)3(PPh3)] (M = Cu (5a), Ag (5b)) were isolated from the reaction of 1 with sources of the fragments [M(PPh3)]+ (M = Cu, Ag). X-ray structure determinations of both species 5 revealed the presence of direct Re – M (M = Cu, Ag) connectivities bridged by carborane beta-B – H – M interactions. In solution the complexes 5 are highly dynamic on the NMR time scale, even at low ( – 90C) temoeratures.

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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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Synthetic Route of 12150-46-8, Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn’t involve a screen. 12150-46-8, C34H28FeP2. A document type is Article, introducing its new discovery.

Reactions between Ru3(mu-dppm)(CO)10 and several reagents have been studied.With allyl bromide, cluster breakup occurs to give binuclear Ru2(mu-Br)(mu-C3H5)(mu-dppm)(CO)4.With Me2S2, binuclear Ru2(mu-SMe)2(mu-dppm)(CO)4 and trinuclear Ru3(mu-H)(mu-SMe)(mu-dppm)(CO)8 are obtained; the X-ray structure of the latter has been determined.With AuCl(PPh3), addition to one Ru-Ru bond gives AuRu3(mu-Cl)(mu-dppm)(CO)8(PPh3).Some data on tertiary phosphine substituted products formed in reactions with PMe3, PPh3, P(C6H4Me-3)3, P(C6H4Me-4)3, P(OMe)3, P(OCH2CF3)3, dppe and Fe(eta-C5H4PPh2)2 are also given.

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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