Extracurricular laboratory:new discovery of Tri-p-tolylphosphine

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1038-95-5, Name is Tri-p-tolylphosphine, molecular formula is C21H21P, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 1038-95-5, Quality Control of: Tri-p-tolylphosphine

Treatment of the tetranuclear gold cluster [Au4{(PPh2)2C2B9H10}2(AsPh3)2] (1), which contains the nido-carboranediphosphine [7,8-(PPh2)2C2B9H10]-, with various tertiary phosphines leads to derivatives [Au4{(PPh2)2C2B9H10}2-(PR3)2] (PR3 = PPh3 (2), P(4-MeC6H4)3 (3), P(4-OMeC6H4)3 (4)). The X-ray crystal structure of complex 4 shows a tetrahedral framework of gold atoms, two of which are chelated by the diphosphine, and two are coordinated to one monophosphine ligand each. These compounds are very stable and are obtained in high yield. MP2 calculations suggest that the two types of chemically nonequivalent gold atoms can be formally assigned as Au(I) (those attached to the arsines or phosphines) and Au(0) (those bonded to the anionic diphosphine) and emphasize the role of correlation in the gold-gold interactions. The compounds are luminescent. The emission is assigned to a gold-centered spin-forbidden transition; the assignment of the oxidation state of the gold centers on this basis leads to results coincident with those obtained by theoretical calculations.

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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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Complexes trans-RIr(CO)L2 (R=Me, CH2CMe3; L=PPh3 or P(p-tolyl)3) are cyclotrimerization catalysts for activated acetylenes.Stoichiometric reaction between C2(CO2Me)2 and trans-Me3CCH2Ir(CO)2 results in the formation of Ir(COCH2CMe3)2,an unusual tetrahedral, 16-electron, iridium(I) complex.An X-ray diffraction study confirms the geometry.The complex Ir(COCH2CMe3)2 crystallizes in the centrosymmetric monoclinic space group P21/c with a=11.125 (2) Angstroem, b=21.725 (6) Angstroem, c=20.889 (5) Angstroem, beta=93.465 (16)deg, V=5039 (2) Angstroem3, and Z=4.Single-crystal X-ray difraction data (Mo Kalpha, 2theta=5-45deg) were collected and the structure solved and refined to RF=6.2percent for those 5196 data with (F0) >3?((F0)) 6?((F0))>.If we regard the eta2-C2(CO2Me)2 ligand as occupying a single stereochemical site (as is usually the case) the molecule is a tetrahedral complex of Ir(I) in which Ir-P=2.334 (3) and 2.314 (3) Angstroem, the Ir-C(acyl) bond length is 1.951 (13) Angstroem, and Ir…cent (center of acetylenic linkage) =1.941 Angstroem.Interligand angles are P(1)-Ir-P(2)=105.20 (10)deg, P(1)-Ir-C(acyl)=94.20 (36)deg, P(1)-Ir-cent =122.80deg, P(2)-Ir-C(acyl)=91.86 (36)deg, P(2)-Ir-cent =123.28deg, and C(acyl)-Ir-cent =111.15deg.The mechanism of the cyclotrimerization reaction involves coordination of an acetylene molecule, an alkyl migration, coordination of a second acetylene molecule, metallacyclopentadiene formation, and cycloaddition of a third acetylene molecule leading to elimination of the derived benzenoid cyclotrimer.

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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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Complexes of the type Me3AlPR2R’ have been synthesised and studied by 1H, 13C, and 31P n.m.r. spectroscopy.The change in 31P chemical shift on co-ordination, <*>(31P), decreases, becoming more negative, with sterically bulkier phosphines and with increasing donor ability.The aluminiummethyl 13C resonance shifts downfield with increasing phosphine steric bulk, and with increased donor ability.Steric effects, however, are found to be the major factor contributing to the changes in both <*>(31P) and methyl 13C chemical shifts.

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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. 1038-95-5, C21H21P. A document type is Article, introducing its new discovery., Formula: C21H21P

The compounds Re(CO)3Cl(L)2, L = triphenylphosphine, tri-p-tolyphosphine, and Re(CO)3Cl(L’), L’ = 1,2-bis(diethylphosphinoethane) are luminescent in solution and in crystalline form when excited between 351 nm and 514 nm at temperatures ranging from 10 K to room temperature.The absorption spectra contain a weak (E ca. 10 M-1 cm-1) band in the visible region of the spectrum between 400 and 500 nm.The lowest energy transition giving rise to these spectroscopic features is assigned to a d-d transition. – Keywords.Rhenium complexes; Electronic emission; Absorption.

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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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Combined TG/DTA techniques have been used to study the thermal decomposition of R3PAuCN (where R is ethyl, cyclohexyl, o-tolyl, m-tolyl, p-tolyl, allyl, cyanoethyl, 1-naphthyl and phenyl) complexes. It was observed that all of these complexes underwant decomposition cum redox reactions in the range of 200-600C with evolution of both trans ligands, which are phosphine and cyanide, leaving metallic gold as a residue. The thermal decomposition of o-Tol3PAuCN has revealed that this is a stepwise process. In the first step decomposition takes place with evolution of phosphine and generation of AuCN, which in second step undergoes a redox reaction to produce metallic gold. The DTA curves have also confirmed these results.

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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 photoinduced electron-transfer reaction of para-substituted triphenylphosphines sensitised by 9,10-dicyano-anthracene (DCA) occurred in acetonitrile containing 2 vol% water to form the corresponding triphenylphosphine oxide. Transient absorption spectral measurements were carried out during 355 nm laser flash photolysis of a mixture of the phosphine and DCA. The electron transfer from the phosphine to singlet excited DCA initiated the reaction. A para substituent on the benzene ring affects the quantum yields of the phosphine radical cation and phosphine oxide. The back electron transfer from the DCA radical anion to the phosphine radical cation governed the quantum yield of the phosphine radical cation. The quantum yield of the phosphine oxide was dependent on the conjugation between the pi-electron of the benzene ring and the n-electron of the phosphorous atom in the phosphine radical cation. The phosphine oxide forms through nucleophilic attack of H2O toward the phosphorus atom of the phosphine radical cation, producing the phosphoranyl radical.

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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. 1038-95-5, Name is Tri-p-tolylphosphine, molecular formula is C21H21P. In a Article,once mentioned of 1038-95-5, Computed Properties of C21H21P

Tetrahedral Mo2Ir2(mu3-CO)(mu-CO)5(CO)4(eta5-C5H5)2 (1) reacted with P(C6H4Me-4)3, P(C6H2Me2-3,5-OMe-4)3, and AsPh3 to afford the substitution products Mo2Ir2(mu-CO)3(CO)6(L)(eta5-C5H5)2 [L = P(C6H4Me-4)3 (3), P(C6H2Me2-3,5-OMe-4)3 (4), AsPh3 (5)] in fair to good yields, while reaction of 1 with HC?CSiPri3 proceeded by insertion into the Mo-Mo bond to give the pseudo-octahedral Mo2Ir2(mu4-eta2-HC2SiPri3)(mu-CO)4(CO)4(eta5-C5H5)2 (6) in fair yield. While MoIr3(mu-CO)3(CO)7(eta5-C5H5) reacted with HC?CSiMe3 to give a complex mixture of thus-far-uncharacterized products, its phosphine substitution product MoIr3(mu-CO)3(CO)5(PPh3)2(eta5-C5H5) reacted with the same alkyne via insertion into a Mo-Ir bond to afford the pseudo-octahedral MoIr3(mu4-eta2-HC2SiMe3)(mu-CO)3(CO)4(PPh3)2(eta5-C5H5) (8) in good yield. Clusters 4, 5 (two isomers), 6 and 8 have been characterized by single-crystal X-ray diffraction studies. Cyclic voltammetric studies of Mo2Ir2(mu-CO)3(CO)6(PPh3)(eta5-C5H5)2 (2), 3-6 and 8 confirmed the tuning of redox potentials upon phosphines/arsine introduction and alkyne modification. IR spectroelectrochemical studies of 2, 6, and 8 suggest decreasing proclivity for bridging carbonyl ligands following oxidation. Variable temperature 31P NMR studies of 3 and 4 revealed interconverting isomers in solution, the structures of which are assigned as analogues of the X-ray diffraction-confirmed isomers of 5. Studies of 2-5 using ns pulses and the open-aperture Z-scan technique revealed that all are optical limiters at wavelengths in the visible region.

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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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Silver nitrate reacts with salicylic acid (salH2) or p-hydroxy-benzoic acid (p-HbzaH2) and equimolar amount of NaOH to yield a white precipitations which are then treated with tri(p-tolyl)phosphine (tptp) or tri(m-tolyl)phosphine (tmtp) to yield the complexes [Ag(tptp)2(salH)] (1), [Ag(tptp)2(p-Hbza)] (2) and [Ag(tmtp)2(salH)] (3). Complexes 1 and 3 are also obtained when aspirin (aspH) is used. The acetic ester of salicylic acid is hydrolyzed to form the complexes 1 and 3. However, when aspirin and tptp are used, a mixture of products was obtained which contains both 1 and an ionic complex of formula {[Ag(tptp)4]+[(salH)-][(CH3)2NCHO)](H2O)} (1a). The complexes were characterized by m.p., e.a., mid-FT-IR, 1H-,31P-NMR, HRMS, UV-vis spectroscopic techniques and X-ray crystallography. Two phosphorus and one carboxylic oxygen atoms form a trigonal planar geometry around Ag(I) ions in complexes 1-3. Complex 1a consists of a [Ag(tptp)4]+ cation and a deprotonated salH- counter anion. The influence of 1-3 on the viability of MCF-7 (breast) and HeLa (cervix) adenocarcinoma cells, is evaluated. DNA binding tests indicate the ability of 1-3 to modify the activity of cells. The binding constants of 1-3 towards calf-thymus DNA, reveal stronger interaction of 2. Changes in fluorescent emission light of ethidium bromide (EB) in the presence of DNA suggest intercalation or electrostatic interactions into DNA for 1 and 3. Docking studies on DNA-complex interactions confirm the binding of 1-3 in the minor groove of B-DNA. Moreover, the influence of 1-3 on the peroxidation of linoleic acid to hydroperoxylinoleic acid by the enzyme lipoxygenase (LOX) was kinetically and theoretically 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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Unprecedented chemoselective reductions of phosphine oxides to phosphines proceed smoothly in the presence of catalytic amounts of specific Br°nsted acids. By utilizing inexpensive silanes, e.g., PMHS or (EtO)2MeSiH, other reducible functional groups such as ketones, aldehydes, olefins, nitriles, and esters are well-tolerated under optimized conditions.

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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 series of luminescent tetranuclear cuboidal copper(I) diynyl complexes, [Cu4(PAr3)4(mu3-eta 1-C?C-C?CR?)4] (Ar=Ph, R?=Ph, C6H4CH3-p, C6H4OCH3-p; Ar=C6H4CH3-p, C6H4F-p, R?=Ph) has been synthesized and characterized. The X-ray crystal structure of [Cu4(PPh3)4(mu3-eta 1-C?C-C?CPh)4] has been determined. The origin of the low-energy emission in the complexes is assigned as derived from a metal-centered 3d94s1 state, mixed with LMCT [diynyl?Cu4] and IL [pi-pi*(diynyl)] 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