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Pyrimidine base ruthenium copper heteronuclear compound and its preparation method and application (by machine translation)

The invention relates to a pyrimidine base ruthenium copper heteronuclear compound, the compounds of the general formula:, wherein R is – H, – CH3 , – OCH3 , – CH2 CH3 , – CH2 CH2 CH3 Or – CH2 CH2 CH2 CH3 ; R1 Is – H or – CH3 ; L is a tertiary phosphine ligand; P is the diphosphine ligand. The compounds can be used as double-metal catalyst to catalyze the reaction of aryl carboxylic acids and olefins, synthetic preparation phthalide derivatives. (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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Synthesis of air-stable zwitterionic 2-phosphiniminium-arenesulfonates

Efficient synthetic methodology for preparation of 2-phosphiniminium-5- methylbenzenesulfonate zwitterions is reported. Staudinger reaction between phosphines and n-propyl 2-azido-5-methylbenzenesulfonates followed by sulfonate ester deprotection using pyridinium tetrafluoroborate/pyridine afforded the zwitterions in excellent yields. This new route directly accesses ortho-substituted-arenesulfonate ligands that incorporate a phosphinimine, a strong sigma-donor.

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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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Convenient synthetic method of functional phosphines under photochemical conditions

Steady-state photolysis of triarylphosphines, Ar3P, under an argon atmosphere in a solvent with the structure CH3X (X = CN, COOC2H5, COCH3) afforded an adduct with the solvent molecule, Ar2PCH2X, in significant amount. This photoreaction is acknowledged as a convenient method to prepare functional phosphines.

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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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Terminal alkyne activation by frustrated and classical lewis acid/phosphine pairs

(Figure Presented) Frustrated and classical Lewis pairs arising from combinations of Lewis acids and phosphines react with terminal alkynes either via C-H activation forming an alkynylborate salt or by addition to alkyne giving a zwitterionic phosphonium borate.

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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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Synthesis, reactivity and solid-state structural studies of new phosphino copper(I) derivatives of hydrotris(3-methyl-2-thioxo-1-imidazolyl)borate

1:1:1 [(R3P)Cu(Tm)] (R = phenyl, cyclohexyl, m- and p-tolyl) or [(R?Ph2P)Cu(Tm)] (R? = methyl or ethyl) triorganophosphine copper(I) adducts, containing the anionic, potential S3-, face-capping ligand hydrotris(3-methyl-1-imidazolyl-2-thione)borate [Tm]-, were synthesised from K[Tm], CuCl and the corresponding P-donor. No phosphine adduct was obtained when tri-o-tolyl-, tribenzyl-phosphine, triphenylarsine and triphenylantimony were reacted with K[Tm] and CuCl, [Cu(Tm)]n being the product obtained always, in strong excess of the phosphorus donor. The probably polynuclear [Cu(Tm)]n is stable towards Hmimt (3-methyl-1-imidazoline-2-thione), NH3, CS2, H2O and CO; it reacts with pyridine (py) to yield the 1:1:1 adduct [(py)Cu(Tm)]. [Cu(Tm)]n also reacts with H2O2 yielding the poorly soluble derivative [Cu(mimt)]n upon breaking of the B-N bond in the azolyl-borate ligand. All of the complexes synthesised were characterised through analytical and spectral (IR, 1H and 31P NMR) measurements. The solid-state structures of [(m-tolyl3P)Cu(Tm)] and [(p-tolyl3P)Cu(Tm)] show the copper atoms to be tetracoordinate with the donor [Tm] behaving as an S3-, face-capping ligand.

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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 diamond-shaped heterometallic cyanide-bridged complex of iron(II) and copper(I), [CpFe(CO)(mu-CN)2Cu(CH3CN)2]2 (1), has been synthesized from the reaction of K[CpFe(CO)(CN)2] and [Cu(CH3CN)4][BF4] in acetonitrile. Upon the addition of 2-4 equivalents of phosphane ligands to complex 1, the coordination geometry of the copper centers can be varied from trigonal planar as in [CpFe(CO)(mu-CN)2Cu(PCy3)]2 (2), to tetrahedral as found in [CpFe(CO)(mu-CN)2Cu(PCy3)2]2 (3). Analogous derivatives containing other phosphane ligands, namely PMe3, P(p-tolyl)3, PMe2Ph, and PPh2Me have been synthesized as well. Prolonged exposure of complex 3 in CH2Cl2 to excess PCy3 has provided the bimetallic complex [CpFe(PCy3)(CN)(mu-CN) Cu(PCy3)2] (4), where the metal aggregate is disrupted and PCy3 has displaced CO at the iron center. Bidentate phosphane analogs of complex 3 have been prepared by adding two equivalents of dcpe [bis(dicyclohexylphosphanyl)-ethane] or dcpp [bis(dicyclohexylphosphanyl)propane] to complex 1. The solid-state structures of several of these diamond-shaped derivatives, in addition to complex 4, have been determined by X-ray crystallography. The overlapping diamond-shaped [Fe2(CN)4Cu2] cores, which form channels within the solids, are blocked by bulky, copper-bound phosphane ligands such as PCy3. However, in the case of the small phosphane PMe3, or the chelating phosphanes dcpe and dcpp, these channels are not blocked by the phosphane ligands; solvent molecules occupy the channels created by the overlapping metal cores instead. Alternatively, the complex [CpFe(CO)(CN)(mu-CN)Cu(dcpm)]2 (13), derived from bis(dicyclohexylphosphanyl)methane(dcpm), possesses two copper(I) centers, each in a distorted trigonal coordination geometry, bridged by two dcpm ligands to form an eight-membered metallacycle with a short CuI···CuI separation of 2.844 A. The third ligand completing each copper’s coordination sphere is a nitrogen-bound bridging cyanide group from a CpFe(CO)(CN)2- anion.

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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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Palladium-catalyzed Pd-aryl/P-aryl interchange reaction was applied in the synthesis of various functionalized arylphosphines. This phosphination used inexpensive, readily available and air stable triarylphosphines as the phosphinating agents. Broad functional groups were compatible including keto, aldehyde, ester, nitrile, ether, chloride, pyridyl and thiophenyl groups. Halides were found to be good promoter for the rates and yields of the reaction.

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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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Pd(0)-Cu(I) catalyzed reactions with certain terminal tertiary propargylic alcohols lead to new arylated products.This abnormal cross-coupling pathway represents another example of aryl migration in transition metal catalyzed reactions.The process is catalytic in palladium if excess triarylphosphine is employed.

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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 systematic study of the reaction between the dinuclear complex [{Rh(mu-Cl)(eta4-COD)}2], (COD = 1,5-cyclooctadiene) with 14 different triarylphosphines is presented. When two equivalents of the phosphine are employed, the main product is the mononuclear complex [RhCl(eta4-COD)(PR3)], with R = 4-(OCH3)C6H4 (1), 4-(CH3)C6H4 (2), C6H5 (3), 4-FC6H4 (4), 4-(CF3)C6H4 (5), 4-ClC6H4 (6), 3-(OCH3)C6H4 (7), 3-(CH3)C6H4 (8), 3-ClC6H4 (9), 2-(OCH3)C6H4 (10), 2-(CH3)C6H4 (11) and R3 = (C6H5)2(C6F5) (12). No mononuclear complex could be isolated with the electron poor phosphines P(C6H5)(C6F5)2 and P(C6F5)3. A chemical equilibrium in solution was observed between the dinuclear and mononuclear species, with the formation of the mononuclear being disfavoured by the use of bulky and electron poor phosphines. The mononuclear complex 11, with the extremely bulky phosphine P(2-CH3C6H5)3, was undetected in solution by NMR, however could be crystallized and its molecular structure determined by X-ray diffraction and compared with the previously reported structures for 3 and 4. For complexes with isosteric phosphines (1-6), an inverse relationship between the coupling constant 1JRh-P and the electronic parameter (chi) of the phosphine was observed.

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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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Synthesis of tetrakis(cyclohexylisocyanide)bis(triPhenylphosphine)cobalt(II) perchlorate. Isolation of cobalt(II) in an unstable stereochemistry

Tetrakis(cyclohexylisocyanide)bis(triphenylphosphine)cobalt(II) perchlorate. [Co(CNC6H11)4(PPh3) 2](ClO4)2, was synthesized and limitedly characterized. This complex was isolated by rapid precipitation and immediate filtration. Under even the most favorable reaction conditions this intrinsically unstable six-coordinate Co(II) complex is still the minor product relative to the thermodynamically-favored five-coordinate Co(I) complex, [Co(CNC6H11)3(PPh3) 2]ClO4. Attempted recrystallization of [Co(CNC6H11)4(PPh3) 2](ClO4)2 yields the five-coordinate Co(II) complex, [Co(CNC6H11)3(PPh3) 2](ClO4)2. Analogous reactions of P(C6H4Me-p)3 and P(C6H4OMe-p)3 with [Co(CNC6H11)5](ClO4)2 in ethanol produced only the [Co(CNC6H11)3(PR3) 2]ClO4 complexes. This six-coordinate Co(II) complex may be an intermediate in the reduction/ligand-substitution reactions for pentakis(organoisocyanide)cobah(II) 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