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Reactivity of a (Fe-NO)-(Fe-NO3) system in the presence of a ferrocene-ferricinium group tethered nearby via a ferrocenyl phosphine linkage (FcP2): crystal structures of <2(mu-FcP2)> and

The nitrosyl dimer <2> (1) reacts with 1,1′-bis(diphenylphosphino)ferrocene (FcP2) to yield 2(mu-FcP2) (2), the structure of which has been determined.The FcP moiety bridges two Fe(NO)2(Cl) groups symmetrically.Oxygenation of 1 in the presence of FcP2 yields (5): Complex 5 catalyses the autoxidation of cyclohexene.It transfers the oxygen atoms of its nitrato groups to phosphines.When allowed to react with an excess of FcP2, 2 gives (4); the subsequent formation of (3) is attributed to th e reaction of 4 with chlorine liberated in situ.The structure of 4 was also determined.Keywords: Iron; Nitrosyl; Ferrocene ligand; Nitrato complex; X-ray diffraction; Oxidation

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Reference£º
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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Microfluidic synthesis of palladium nanocrystals assisted by supercritical CO2: Tailored surface properties for applications in boron chemistry

On the surface: A library of organic-inorganic hybrid palladium nanocrystals was synthesized using continuous supercritical microfluidic technology. The nanocatalysts show moderate to excellent activities towards CArB and CArCAr bond-forming reactions, thus illustrating the relationship between surface properties and modulated catalytic activity.

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Reference£º
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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Process for the preparation of adapalene

A process for the preparation of a compound of formula (I), or a salt thereof wherein R is H, C1-C8 alkyl, aryl or aryl-C1-C8 alkyl; comprising the reaction between a compound of formula (II) wherein R1 and R2 are independently hydrogen, C1-C8 alkyl, aryl, aryl-C1-C8 alkyl, or R1 and R2, taken together, form a ?(CH2)m?V?(CH2)n? group, in which V is NR3 or C(R3)2 wherein R3 is hydrogen, C1-C8 alkyl, aryl or aryl-C1-C8 alkyl; and m and n, which can be the same or different, are 1 or 2; with a compound of formula (III) in which R4 and R5 are independently C1-C8 alkyl, aryl or aryl-C1-C8 alkyl; in the presence of a Ni (II) salt, an organic ligand and a basic agent, to obtain a compound of formula (I) wherein R is C1-C8 alkyl, aryl or aryl-C1-C8 alkyl and, if desired, its conversion to a compound of formula (I) wherein R is hydrogen or to a salt thereof.

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Reference£º
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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Evaluation of Bis(phosphine) Ligands for Ethylene Oligomerization: Discovery of Alkyl Phosphines as Effective Ligands for Ethylene Tri- And Tetramerization

Fifty-three bis(phosphines) were evaluated as ligands for chromium-catalyzed ethylene tetramerization in a high-throughput reactor. Selected ligands previously reported in the literature gave high activities with expected selectivities when evaluated under our reactor conditions. While the majority of ligands evaluated gave low activity catalysts that produced mostly high-density polyethylene (HDPE), alkyl phosphines were unexpectedly identified as a promising ligand class. In particular, the MeDuPhos ligand led to an active catalyst that produced 81.8 wt % alpha-olefins (50.0 wt % 1-octene, 31.8 wt % 1-hexene) and 3.5 wt % HDPE, approaching the selectivity of the state-of-the-art i-Pr-PNP ligand.

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Reference£º
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 Structural Intermediate in the Assembly of Gold-Phosphine Chain Polymers

The reaction of 1,1′-bis(diphenylphosphine)ferrocene, fdpp, with a twofold excess of AuCl(SMe2) in dichloromethane yields bis(chloro<1,1'-bis(diphenylphosphine)ferrocene-P,P'>gold)-dichloromethane (1/2), <(AuCl)2(mu-Fe(C17H14P)2)>*2CH2Cl2.The coordination at the Au atoms in the dimeric complex is distorted, involving three P-Au bonds and a long Au…Cl contact.The fdpp ligand adopts both chelating and bridging binding modes.

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Reference£º
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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Redox Induced Configurational Isomerization of Bisphosphine-Tricarbonyliron(I) Complexes and the Difference a Ferrocene Makes

The tricarbonyliron (TCFe) complexes Fe(CO)3(dppf) and Fe(CO)3(dppp), where dppf = 1,1?-bis(diphenylphosphino)ferrocene and dppp = 1,3-bis(diphenylphosphino)propane, exhibit redox activity that induces configurational isomerization. The presence of the ferrocenyl (Fc) group stabilizes higher oxidized forms of TCFe. Using spectroelectrochemistry (IR, UV-vis, Moessbauer, and EPR) and computational analysis, we can show that the Fc in the backbone of the dppf ligand tends to form a weak dative bond to the electrophilic TCFeI and TCFeII species. The open shell TCFeI intermediate was stabilized by the distribution of spin between the two Fe centers (Fc and TCFe), whereas lacking the Fc moiety resulted in highly reactive TCFeI species. The [Fe(CO)3(dppf)]+ cation adopts two possible configurations, square-pyramidal (without an Fe-Fe interaction) and trigonal-bipyramidal (containing an Fe-Fe interaction). The two configurations are in equilibrium with the trigonal-bipyramidal configuration being enthalpically favored (DeltaH = -7 kJ mol-1). There is an entropic penalty (DeltaS = -20 J mol-1) due to tilting of the Cp (cyclopentadienide) rings of the dppf moieties by ?8. Additionally, the terminal iron hydride [FeH(CO)3(dppf)]BF4 was formed by protonation with a strong acid (HBF4¡¤Et2O).

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Reference£º
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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Chiral Platinum(II) Complexes Featuring Phosphine and Chloroquine Ligands as Cytotoxic and Monofunctional DNA-Binding Agents

Chiral molecules in nature are involved in many biological events; their selectivity and specificity make them of great interest for understanding the behavior of bioactive molecules, by providing information about the chiral discrimination. Inspired by these conformational properties, we present the design and synthesis of novel chiral platinum(II) complexes featuring phosphine and chloroquine ligands with the general formula [PtCl(P)2(CQ)]PF6 (where (P)2 = triphenylphosphine (PPh3) (5), 1,3-bis(diphenylphosphine)propane (dppp) (6), 1,4-bis(diphenylphosphine)butane (dppb) (7), 1,1?-bis(diphenylphosphine)ferrocene (dppf) (8), and CQ = chloroquine] and their precursors of the type [PtCl2(P)2] are described. The complexes were characterized by elemental analysis, absorption spectroscopy in the infrared and ultraviolet-visible (UV-vis) regions, multinuclear (1H, 13C, 31P, 15N, and 195Pt) NMR spectroscopy, cyclic voltammetry, and mass spectrometry (in the case of chloroquine complexes). The interactions of the new platinum-chloroquine complexes with both albumin (BSA), using fluorescence spectroscopy, and DNA, by four widely reported methods were also evaluated. These experiments showed that these Pt-CQ complexes interact strongly with DNA and have high affinities for BSA, in contrast to CQ and CQDP (chloroquine diphosphate), which interact weakly with these biomolecules. Additional assays were performed in order to investigate the cytotoxicity of the platinum complexes against two healthy cell lines (mouse fibroblasts (L929) and the Chinese hamster lung (V79-4)) and four tumor cell lines (human breast (MDA-MB-231 and MCF-7), human lung (A549), and human prostate (DU-145)). The results suggest that the Pt-CQ complexes are generally more cytotoxic than the free CQ, showing that they are promising as anticancer drugs.

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Reference£º
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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Photochemical Reaction of Tricarbonyl(eta-methylcyclopentadienyl)manganese(I), , with 1,1′-Bis(diphenylphosphino)ferrocene, (dppfe), and X-Ray Molecular Structure Analysis of

Photochemical reaction of MeCpMn(CO)3 with (Ph2PC5H4)2Fe, (dppfe), was conducted in benzene.From the reaction mixture, the title compound was isolated and its molecular structure was solved by X-ray analysis. ?(CO) peak at 1810 cm-1 of the title compound was clarified to be originated from the terminal carbonyl.Temperature-dependent 1H NMR spectra were also measured for the title compound.

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Reference£º
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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Synergy between Experimental and Computational Chemistry Reveals the Mechanism of Decomposition of Nickel-Ketene Complexes

A series of (dppf)Ni(ketene) complexes were synthesized and fully characterized. In the solid state, the complexes possess eta2-(C,O) coordination of the ketene in an overall planar configuration. They display similar structure in solution, except in some cases, the eta2-(C,C) coordination mode is also detected. A combination of kinetic analysis and DFT calculations reveals the complexes undergo thermal decomposition by isomerization from eta2-(C,O) to eta2-(C,C) followed by scission of the C=C bond, which is usually rate limiting and results in an intermediate carbonyl carbene complex. Subsequent rearrangement of the carbene ligand is rate limiting for electron poor and sterically large ketenes, and results in a carbonyl alkene complex. The alkene readily dissociates, affording alkenes and (dppf)Ni(CO)2. Computational modeling of the decarbonylation pathway with partial phosphine dissociation reveals the barrier is reduced significantly, explaining the instability of ketene complexes with monodentate phosphines.

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Reference£º
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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Process for synthesis of acrylic acid precursors via hydroformylation of vinyl ether

A process is disclosed for the preparation of acrylic acid precursors by a hydroformylation process which comprises reacting a vinyl ether with carbon monoxide and hydrogen in the presence of a catalyst comprising a rhodium carbonyl compound and a phosphine ligand at a mild temperature and pressure until there is substantial formation of the intermediate 2- and 3-ethoxypropanals, followed by oxidation of said aldehydes and pyrolysis to said acrylic acid.

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Reference£º
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