Triphenylphosphine Complexes Research Articles

Equilibrium and enthalpy measurements on the complex formation between silver(I) and tri- and dialkylphosphines and tributylstibine in pyridine solution

The stabilities and the heats of formation of silver(I) tributylphosphine, tricyclohexylphosphine, dicyclohexylphosphine, and tributylstibine complexes have been determined in pyridine, by means of potentiometric and calorimetric measurements. Three mononuclear complexes are formed with tributylphosphine, while only two mononuclear complexes are formed with the other ligands, within the ranges of concentration available. All complexes are formed in strongly exothermic reactions, while the entropy changes are negative. The stabilities of the silver(I) phosphine complexes show a strong correlation with some physical parameters of the ligands, such as the dipole moments, and the acid constants in aqueous solution, and the electronic parameters, v, determtned IR-spectroscopically in the Ni(CO) 3L complexes, L=phosphine or phosphite, in dichloromethane. The stabilities of the trialkylphosphine complexes are higher than the triphenylphosphine complexes, and the stabilities of alkylphosphines are in the order (primary) < secondary < tertiary phosphines.

Lewis-Base Adducts of Group-11 Metal(I) Compounds. XXX. 3:1 Complexes of Triphenylphosphine With Silver(I) Halides

3 : 1 adducts of triphenylphosphine, PPh3, with silver halides, AgX, have been characterized for chloride, bromide and iodide by single-crystal X-ray structure determinations, the chloride as its diacetone solvate. Crystals of the chloride, [(PPh3)3AgCl].2(CH3)2CO, are triclinic, P1, a 13.654(4), b 14.059(4), c 13.970(4) �, α 84.82(2), β 87.71(2), γ 75.68(2)�, Z 2; the structure was refined to a residual R of 0.061 for No = 2428 independent 'observed' reflections. Crystals of the bromide, [(PPh3)3AgBr], are trigonal, P3, a l9.366(6), c 10.787(6) �, Z 3, R was 0.054 for No = 2362. Crystals of the iodide, [(PPh3)3AgI], are monoclinic, P2l/n, a 18.993(8), b 13.807(4), c 17.781(8) �, β 96.11(4)�, Z 4; R was 0.042 for No = 3691. Ag-Cl, Br, I respectively are 2.533(4), 2.671(6)-2.691(4) and 2.858(1) �. Ag-P for each of the three structures respectively lie in the ranges 2.558(5)-2.582(4), 2.528(3)-2.549(7)and 2.544(2)-2.780(3) �.

Polymeric cofactors which accelerate homogeneous rhodium(I) and ruthenium(II) catalyzed hydrogenations of alkenes

AbstractPolymeric reagents prepared by exchanging silver(I) for H+ on a macroreticular polystyrene sulfonate ion exchange resin are shown to be capable of selectively absorbing triphenylphosphine from solutions of triphenylphosphine complexes of rhodium(I) and ruthenium(II). Absorption of triphenylphosphine during alkene hydrogenations catalyzed by RhCl(PPh3)3, RuCl2(PPh3)3 and RuHCl(PPh3)3 led to increased hydrogenation rates in hydrogenation of 1‐hexene and other alkenes. Addition of this silver(I) polystyrene sulfonate to alkene hydrogenations catalyzed by HRh(CO) (PPh3)3, RuH2(PPh3)3 and RuH(OCOCH3) (PPh3)3 also led to modest rate accelerations. Catalyst activations seen in these alkene hydrogenations were shown to be due in some cases to triphenylphosphine absorption. In other cases, HCl or HCl plus triphenylphosphine absorption was responsible for the formation of a more active catalyst solution.

ChemInform Abstract: Regioselective Ring Cleavage of Oxiranes Catalyzed by Organotin Halide‐ Triphenylphosphine Complex.

AbstractAus den Epoxiden (I) erhält man mit dem Benzoylchlorid (II) in Gegenwart von Dibutylzinndichlorid und Triphenylphosphin die isomeren Chlorhydrinester (III) und (IV).

Laser deposition of a metal from triphenylphosphine complexes of univalent gold

Laser deposition of Au from triphenyl complexes RAuL of univalent gold on some semiconductor and insulator substrates was realized experimentally. A metal deposit of ~1μ transverse size was observed in a laser projection microscope.

Regioselective ring cleavage of oxiranes catalyzed by organotin halide - triphenylphosphine complex

Vicinal chloroesters are formed in high yield from the reaction of oxiranes and benzoyl chloride in the presence of organotin halide - triphenylphosphine complex with enhanced regioselectivity in oxirane ring cleavage.

Studies on thermal stability and knot formation in the TG curves of Co(III) model complexes

TG studies of vitamin B12 coenzyme model complexes, BrCo(diacetylmonoximeiminatodiacetylmonoximatoiminobenzene-1,6)L have been carried out with different heating rates and sample sizes. The trans ligand, L, is bromine, imidazole, methylimidazole, pyridine or triphenylphosphine. The decompositions of the complexes (except for the triphenylphosphine complex) are associated with the formation of a knot at the point of completion of the inflection of the TG curve at a heating rate of 20 deg/min; such a phenomenon is not observed for rates of 10 and 5 deg/min. The formation of a knot with increase in weight and decrease in temperature is attributed to the transition from high-energy six-coordinate Co(III) species to low-energy five-coordinate Co (II) species. The triphenylphosphine complex is found to deviate from these characteristics of decomposition.

New seven-coordinate mixed triphenylphosphine, arsine and antimony complexes of molybdenum(II) and tungsten(II)

New seven-coordinate mixed triphenylphosphine, arsine and antimony complexes of molybdenum(II) and tungsten(II)

ChemInform Abstract: MONONUCLEAR η6‐P‐CYMENEOSMIUM(II) COMPLEXES AND THEIR REACTIONS WITH AL2ME6 AND OTHER METHYLATING REAGENTS

AbstractDas aus Na‐hexachloroosmiat(IV) und α‐Phellandren in siedendem abs.

ChemInform Abstract: N‐ALLYLATION OF IMIDES CATALYZED BY PALLADIUM(0)

AbstractPcl(O)‐PPh3‐Komplexe katalysieren den Allylaustausch zwischen z.B. den Estern (II) und (I) [Bildung von (III)], ebenso zwischen Allyl‐phenyl‐ether und (I) und zwischen O‐Allyl‐isoharnstoff und (I) [(IIIa)‐Ausb.: 84% bzw. 74°C /o].

Mononuclear η6-p-cymeneosmium(II) complexes and their reactions with Al2Me6and other methylating reagents

An improved-yield synthesis of the η6-p-cymeneosmium(II) chloride complex [(p-MeC6H4CHMe2)2Os2Cl4](1) has allowed the development of the chemistry of the mononuclear complexes, [(p-MeC6H4CHMe2)OsLCl2](2)[L = CO, CNCMe3, Me2SO, PMe3, PPh3, or P(OPh)3]. These gave [(p-MeC6H4CHMe2)OsL(Me)Cl](3)(L = CO, CNCMe3, Me2SO, or PMe3) with Al2Me6. Reaction of [(p-MeC6H4CHMe2)Os(Me2SO)(Me)Cl] with L′[PPh3 or P(OPh)3] gave the complex [(p-MeC6H4CHMe2)OsL′(Me)Cl]. Al2Me6 reacted with [(p-MeC6H4CHMe2)OsL′Cl2] to give chiefly the ortho-metallated complexes [(p-MeC6H4CHMe2)Os{PPh2(o-C6H4)}X](5)(X = Cl), (6)(X = Me), and [(p-MeC6H4CHMe2)Os{P(OPh)(OC6H4-o)2}](8); however, the triphenylphosphine complex also gave the mono- and the di-methyl complexes [(p-MeC6H4CHMe2)Os(PPh3)(Me)X](X = Cl or Me). The complexes have been characterised by their i.r., 1H, 13C, and 31P n.m.r. spectra and their e.i. mass spectra. The p-cymene ring remains η6-bonded throughout these reactions and appears quite difficult to displace.

N-Allylation of Imides Catalyzed by Palladium(0)

Abstract Palladium(0)–triphenylphosphine complexes catalyzed the allylic exchange reaction of allylic esters, phenyl ethers, and isoureas with imides such as phthalimide to give N-allylic products. Among them, O-allylic isoureas were most effective in exchanging the allylic group of more complex structure. N-Allylic derivatives were also obtained by the telomerization of butadiene or allene with phthalimide catalyzed by a palladium(0) species.

New catalyst for the synthesis of dialkyl ketones from olefins, carbon monoxide, and hydrogen

Dialkyl ketones are formed in mild conditions (30–70°C, 1 atm) from H2+CO + C2H4 or C3H6 in aqueous trifluoroacetic acid solutions of a PdII triphenylphosphine complex.

Cyanomethyl derivatives of gold

1. Triphenylphosphine complexes of cyanomethylgold and dichlorocyanomethylgold have been synthesized. 2. The chemical properties of aurated acetonitrile were typical for σ organogold compounds but aurated dichloroacetonitrile recalled the chemical behavior of complex gold halides 3. The gold atom in the molecule of dichlorocyanomethyl (triphenylphosphine) gold has linear coordination, the bond lengths and angles were typical for organic complexes of univalent gold.

Liquid-phase codimerization of ethylene with propylene on nickel carbonyl triphenylphosphine complex anchored on surface of aluminum oxide

1. The catalytic system Ni(CO)x(PPh3)y/A12O3-Et3Al2Cl3 (x + y=4) is active at 40°C in copolymerization of ethylene with propylene over a broad range of monomer concentrations. 2. The molecular weight distribution and structural composition of the products depends on the ratio γo=[C3H6]/[C2H4]o. The maximum yield of C5 olefins is 45% with γo=7–32. 3. Under conditions of codimerization, ethylene accelerates the dimerization of propylene quite substantially.

Crystalline-state reaction of cobaloxime complexes by X-ray exposure. VI. Racemization of tributyl- and triphenylphosphine complexes

Crystalline-state reaction of cobaloxime complexes by X-ray exposure. VI. Racemization of tributyl- and triphenylphosphine complexes

Catalytic reactions involving butadiene III. Oligomerisation with cationic bis(triphenylphosphine)(η3-allyl) complexes

Abstract The bis(triphenylphosphine)(η 3 -crotyl)nickel cation is a catalyst precursor for the oligomerisation of butadiene to cyclic or linear dimers. Polymers and oligomers are also produced in variable amounts. The product distributions depend strongly on the type of solvent used and on the nature of co-catalysts. In the aprotic polar solvent DMF, the starting complex undergoes disproportionation, leading finally to a zerovalent nickel-phosphine catalyst. In protic solvents (alcohols) a cationic hydridonickel-phosphine catalyst is produced, but addition of sodium methoxide induces the formation of the zerovalent nickel-phosphine, therefore accounting for the changes in product selectivities.

Reactions of ruthenium triphenylphosphine complexes with diazadienes. Part 3. Preparation, characterization, X-ray crystal structure, and reactivity of a formally ruthenium(0) tris(α-di-imine) complex

The reaction between [RuH2(PPh3)4] or [RuH(C6H4PPh2)(PPh3)2(C2H4)] and 3 equivalents of the α-di-imine p-MeOC6H4NCHCHNC6H4OMe-p(L) produces black crystalline [RuL3]. This complex is diamagnetic below –10 °C and becomes paramagnetic at higher temperature. The X-ray crystal structure and u.v. spectra show that the three ligands are equivalent. The complex can be considered as containing 20-electron ruthenium(0). It is rapidly oxidized by molecular oxygen to [RuL3]2+. Crystals of [RuL3]·C6H5CH3 are triclinic, space group P, with a= 14.269(2), b= 24.999(2), c= 13.967(2)A, α= 92.04(1), β= 95.01(1), γ= 104.33(1)°, and Z= 4. The structure was refined using 3 867 ‘observed’ reflections to a final R value of 0.109.

ChemInform Abstract: TRIPHENYLPHOSPHINE COMPLEXES OF PLATINUM(0); THEIR ABSORPTION AND EMISSION SPECTRA AND LUMINESCENCE LIFETIMES

Chemischer InformationsdienstVolume 13, Issue 3 Physical Organic Chemistry ChemInform Abstract: TRIPHENYLPHOSPHINE COMPLEXES OF PLATINUM(0); THEIR ABSORPTION AND EMISSION SPECTRA AND LUMINESCENCE LIFETIMES S. SOSTERO, S. SOSTEROSearch for more papers by this authorM. LENARDA, M. LENARDASearch for more papers by this authorO. TRAVERSO, O. TRAVERSOSearch for more papers by this authorW. J. REED, W. J. REEDSearch for more papers by this authorT. J. KEMP, T. J. KEMPSearch for more papers by this author S. SOSTERO, S. SOSTEROSearch for more papers by this authorM. LENARDA, M. LENARDASearch for more papers by this authorO. TRAVERSO, O. TRAVERSOSearch for more papers by this authorW. J. REED, W. J. REEDSearch for more papers by this authorT. J. KEMP, T. J. KEMPSearch for more papers by this author First published: January 19, 1982 https://doi.org/10.1002/chin.198203042Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume13, Issue3January 19, 1982 RelatedInformation

Triphenylphosphine complexes of cadmium(II) perchlorate, nitrate, and trifluoroacetate preparation, characterization, and spectral studies

1:2 complexes, CdX2(PPh3)2, where X = ClO4, NO3, CF3CO2 and 1:1 complex, Cd(CF3CO2)2PPh3, have been isolated and characterized by elemental analysis and by vibrational and 31P—{lH} nmr spectral measurements. Conductance measurements show that the complexes behave as non-ionic species in dichloromethane. The vibrational spectra of the perchlorato complex are consistent with a six-coordinate structure in the solid state as well as in solution but it is difficult to deduce the structures of the nitrato and trifluoroacetato complexes from the spectral data. Assignments for the metal–ligand stretching frequencies for all the four complexes have been proposed. The 3lP—{1H} nmr spectra of the four complexes have been discussed. Formation of the 1:3 and 1:4 complexes, Cd(ClO4)2(PPh3)3 and Cd(ClO4)2(PPh3)4, in solution, has also been established by 31P—{lH} nmr spectral measurements.