Archives for Chemistry Experiments of 1038-95-5

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CYCLOMETALLATION REACTIONS IN COMPLEXES OF THE TYPE Rh(oq)(CO)(P(o-BrC6F4)Ph2) III. SYNTHESIS OF THE COMPOUNDS cis-Rh(oq)Br(P(o-C6F4)Ph2)L. THE MOLECULAR STRUCTURE OF cis-Rh(oq)Br(P(o-C6F4)Ph2)(PPh3) (oq = 8-oxyquinolinate)

The reaction of Rh(oq)(CO)(PCBr) (PCBr = P(o-BrC6F4)Ph2; oq = 8-oxyquinolinate) in refluxing toluene in the presence of Et4NBr (1/4 molar ratio)gives , PC = P (o-C6F4)Ph2, in practically quantitative yield.The water molecule is readily displaced by various P-donor ligands to give complexes of general formula (PR3 = PPh3, P(p-MeC6H4)3, P(p-MeOC6H4)3, P(p-FC6H4)3, P(OMe)3 and P(OPh3).The molecular structure of the compound has been determined by X-ray methods.Crystals of the title compound are monoclinic, space group P21/n with unit cell dimensions a 11.273(4), b 20.087(8), c 17.471(7) Angstroem and beta 102.15(8) deg.The final R for 2304 diffractometer data refined by least-squares is 0.0468.The compound has a distorted octahedral coordination with the phosphorus atoms in a cis disposition.The Rh-P bond lengths are significantly different.The P atom of the metallated phosphine, which is trans to N, has a Rh-P distance of 2.308(4) Angstroem, while the PPh3, which is trans to C, has a Rh-P distance of 2.422(4) Angstroem.The most distorted angles around the rhodium atom are P(1)-Rh-P(2) 104.7(1) deg and P(1)-Rh-C(1) 69.2(3) deg.

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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 second aryl phosphate chloride compounds (by machine translation)

The present invention discloses a two-aryl phosphate the preparation of acid chloride method, which belongs to the field of organic synthesis. The method uses three aryl phosphate as the starting material, trifluoro methane sulfonic acid catalyst is zinc, after reaction with phosphorus trichloride obtained through distillation aryl phosphate chloride compound. The invention compared with the prior art high reaction yield, after treatment is simple, with substituent is particularly suitable for the second aryl phosphate the preparation of acid chloride, is more suitable for industrial production. The prepared aryl phosphate chloride compounds can be used for synthesizing the ligand of metal catalyst, is applied to the organic photoelectric material and medical fields. (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

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Binap as an 8e arene-mono-phosphine donor to Ru(II)

The reaction of the cationic hydride complex [RuH(eta6- benzene)(Binap)]CF3SO3 with PPh3 at 80C afforded complex 4 in excellent yield. The reaction with tri(p-tolyl) phosphine afforded an analogous compound, 5. After loss of the complexed benzene, the Ru-cation generated chooses to stabilize itself by coordinating the proximate naphthyl ring at the expense of one of the two phosphorus donors. The solid-state structure of 4 is reported and reveals that the eta6 arene is strongly distorted towards a eta4-mode.

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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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Atom-efficient Pd-catalyzed cross-couplings of chloroarenes with triarylbismuth reagents

Various Pd-catalyzed protocols have been developed for the atom-efficient cross-coupling of chloroarenes with triarylbismuth reagents. Using the developed protocols, an efficient synthesis of unsymmetrical biaryls in good to excellent yields was achieved by employing electron-deficient chloroarenes and a range of triarylbismuth reagents.

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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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PREPARATION AND CATALYTIC ACTIVITY OF CATIONIC RHODIUM TETRAFLUOROBENZOBARRELENE COMPLEXES WITH NITROGEN AND PHOSPHORUS DONOR LIGANDS

The preparation and properties of twenty five new cationic rhodium(I) complexes with tetrafluorobenzobarrelene and mono- or bidentate nitrogen or phosphorus donor ligands are described.The complexes with tertiary phosphines show high selectivities in the hydrogenation of 1-hexyne and several diolefins towards monoolefins.The dependence of the reduction rate upon the basicity of the phosphine has been studied.

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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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Ruthenium-stabilized low-coordinate phosphorus atoms. p-cymene ligand as reactivity switch

A detailed comparative study of the structural and spectroscopic features and of the reactivity of ruthenium phosphinidene complexes (eta6- Ar)(PCy3)Ru(PMeS*) (2a, Ar = p-cymene; 2b, Ar = benzene) has been undertaken. The structures of complexes 2a and 2b have been determined by single-crystal X-ray diffraction and display similar features. Both compounds possess identical chemical behavior toward Broensted acids such as HBF 4: protonation of the phosphinidene ligand yields the new cationic complexes [(eta6-Ar)(PCy3)Ru(PHMes*)]BF 4 (3aBF4, Ar = p-cymene; 3bBF4, Ar = benzene), which exhibit an unprecedented phosphenium-bearing hydrogen substituent. 3aBF4 has been characterized using X-ray diffraction techniques. The lone pair of the phosphorus atom of the phosphinidene ligand remains also accessible to the Lewis acid BH3: the reactions of 2a and 2b with borane give the adducts (eta6-Ar)(PCy3)Ru[P(BH 3)MeS*] (4a, Ar = p-cymene; 4b, Ar = benzene). In the presence of the larger borane BPh3, no reaction occurs until water is introduced in the reaction vessel. This results in the generation of [(eta6-Ar) (PCy3)Ru(PHMes*)]BPh3OH (3aBPh3OH, Ar = p-cymene; 3bBPh3OH, Ar = benzene) presumably through protonation of 2a and 2b by the previously unknown adduct H2O-BPh3. Phosphinidene complexes react also with electrophilic alkylating reagents such as organic iodides provided the alkyl substituent is small. Treatment of 2a and 2b with 1 equiv of methyliodide leads to the alkylation at the phosphinidene center and yields the phosphenium complexes [(eta6-Ar)(PCy 3)Ru(PMeMes*)]I (5a, Ar = p-cymene; 5b, Ar = benzene). Examination of the reactivity toward electron-rich reagents such as the alkynes RCCH (R = Me3Si, Ph) yields unexpected results: 2a instantaneously reacts to generate phosphaindane complexes 6 and 7, whereas no reaction occurs when using 2b. A detailed kinetic study provides evidence for a dissociative mechanism involving the release of the phosphine ligand in 2a and explains its specificity. The /?-cymene ligand in 2a acts as a reactivity switch due to the higher steric hindrance of this arene.

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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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Wide range of pKa values of coordinated dihydrogen. Synthesis and properties of some eta2-dihydrogen and dihydride complexes of ruthenium

The new ruthenium hydride complexes CpRuH(L) (L = PR2CH2CH2PR2, R = p-CF3C6H4 (dtfpe) or R = p-MeOC6H4 (dape)) were prepared by reaction of NaOMe with CpRuCl(L), which were obtained by treating CpRuCl(PPh3)2 with L. Similarly, Cp*RuH(L) (L = dppm, (PMePh2)2) were prepared from the reaction of NaOMe with Cp*RuCl(L) obtained from the reaction of Cp*RuCl2 with L in the presence of Zn. Protonation of CpRuH(L) (L = dtfpe, dape) and Cp*RuH(dppm) with HBF4-Et2O produces mixtures of [CpRu(H)2(L)]+ and [CpRu(eta-H2)(L)]+, and [Cp*Ru(H)2(dppm)]+ and [Cp*Ru-(eta2-H2)(dppm)]+. The pKa values of the dihydrogen/dihydride complexes [CpRuH2(L)]+ (L = dtfpe, dppm, dppe, (PPh3)2, dppp, dape) and [Cp*RuH2(L)]+ (L = dppm, (PMePh2)2) are determined by studying acid/base equilibria by 1H and 31P NMR spectroscopy in both CH2Cl2 and THF. The electrochemical properties of the monohydrido complexes CpRuH(L) and Cp*RuH(L) are reported. Peak potentials for oxidation of these monohydrides and pKa values of the cationic complexes are linearly related for all the complexes with a dihydrogen form: pKa(Ru(H2)+) = -10.7Epa(RuH+/RuH) + 13.0. As expected eta2-H2 acidity decreases as the parent hydride becomes easier to oxidize. The related complexes with just a dihydride form, [CpRu(H)2(L)]+ (L = (PPh3)2, dppp) and [Cp*Ru(H)2(PMePh2)2]+, give a similar trend. Acidity constants have been determined for both tautomers when they observed; the pKa of the eta2-H2 form is ?0.3 pKa unit less (more acidic) than that of the (H)2 form for the complexes with L = dtfpe, dppe, and dape but is 0.4 unit greater for [Cp*RuH2(dppm)]+. The acidities of the two tautomers are similar because their concentrations are similar and they have the same monohydrido conjugate base. Other trends in pKa, 1J(HD), and deltaRu(H2) values of dihydrogen complexes and ratio of dihydride to dihydrogen tautomers and the peak potentials for oxidation of the monohydrido complexes are presented. These correlations are shown to be of value in explaining/predicting the propensity of dihydrogen to undergo heterolytic cleavage. Extremes in pKa values of such cyclopentadienylruthenium(Il) complexes are expected for [Cp*RuH2(dmpe)]+ (pKa ? 12) and [CpRuH2(CO)2]+ (pKa ? -6).

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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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Highly stable noble metal nanoparticles dispersible in biocompatible solvents: Synthesis of cationic phosphonium gold nanoparticles in water and DMSO

In this work, we report the synthesis of novel cationic phosphonium gold nanoparticles dispersible in water and dimethyl sulfoxide (DMSO) for their potential use in biomedical applications. All the cationic-functionalising ligands currently reported in the literature are ammonium-based species. Here, the synthesis and characterisation of an alternative system, based on phosphonioalkylthiosulfate zwitterions and phosphonioalkylthioacetate were carried out. We have also demonstrated that our phosphonioalkylthiosulfate zwitterions readily disproportionate into phosphonioalkylthiolates in situ during the synthesis of gold nanoparticles produced by the borohydride reduction of gold(iii) salts. The synthesis of the cationic gold nanoparticles using these phosphonium ligands was carried out in water and DMSO. UV-visible spectroscopic and TEM studies have shown that the phosphonioalkylthiolates bind to the surface of gold nanoparticles which are typically around 10 nm in diameter. The resulting cationic-functionalised gold nanoparticles are dispersible in aqueous media and in DMSO, which is the only organic solvent approved by the U.S. Food and Drug Administration (FDA) for drug carrier tests. This indicates their potential future use in biological applications. This work shows the synthesis of a new family of phosphonium-based ligands, which behave as cationic masked thiolate ligands in the functionalisation of gold nanoparticles. These highly stable colloidal cationic phosphonium gold nanoparticles dispersed in water and DMSO can offer a great opportunity for the design of novel biorecognition and drug delivery 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

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The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 1038-95-5 is helpful to your research., Application of 1038-95-5

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SYNTHESIS AND STUDY OF NEW CARBONYL COMPLEXES OF RHODIUM(I) WITH (S,S)-DONOR LIGANDS AND TERTIARY PHOSPHINES

The reaction of the dimeric diolefin-rhodium(I) chloride complexes with (S,S)-donor ligands gives complexes of the type .These react with carbon monoxide with displacement of the diolefin and formation of .The carbon monoxide can be partly or completely replaced (depending upon the reaction conditions) by addition of triarylphosphines to yield complexes of the type and .

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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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Perfluoroaryl Azide Staudinger Reaction: A Fast and Bioorthogonal Reaction

We report a fast Staudinger reaction between perfluoroaryl azides (PFAAs) and aryl phosphines, which occurs readily under ambient conditions. A rate constant as high as 18 m?1 s?1 was obtained between methyl 4-azido-2,3,5,6-tetrafluorobenzoate and methyl 2-(diphenylphosphanyl)benzoate in CD3CN/D2O. Furthermore, the iminophosphorane product was stable toward hydrolysis and aza-phosphonium ylide reactions. This PFAA Staudinger reaction proved to be an excellent bioothorgonal reaction. PFAA-derivatized mannosamine and galactosamine were successfully transformed into cell-surface glycans and efficiently labeled with phosphine-derivatized fluorophore-conjugated bovine serum albumin.

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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