13965-03-2Relevant articles and documents
ELECTROCHEMICAL BEHAVIOUR OF Pd(0) AND Pd(II) COMPLEXES WITH TRIPHENYLPHOSPHINE IN DIMETHYLFORMAMIDE.
Vasini, E. J.,Giordano, M. C.
, p. 205 - 212 (1988)
The electrochemical behaviour of a palladium electrode in the presence of ligands such as chloride ions and triphenylphosphine (PPh//3) in dimethylformamide (DMF) solution, and that of a DMF solution of palladium chloride in the presence of the same ligands were investigated by cyclic voltammetry and chronopotentiometric techniques. The PdCl//2-ligands solution systems form a well-defined redox couple at high ( greater than 4) PPh//3 to Cl** minus concentration ratio. The redox couple corresponds to a quasi-reversible surface process, whereas the anodic dissolution of Pd in the presence of ligands is better described as a catalytic reaction with an irreversible charge transfer.
Metal coordination mediated reversible conversion between linear and cross-linked supramolecular polymers
Wang, Feng,Zhang, Jinqiang,Ding, Xia,Dong, Shengyi,Liu, Ming,Zheng, Bo,Li, Shijun,Wu, Ling,Yu, Yihua,Gibson, Harry W.,Huang, Feihe
, p. 1090 - 1094 (2010)
(Figure Presented) The dynamic duo: Different topologies of dynamic supramolecular polymers, such as linear (see picture, left) and crosslinked species (right), can be reversibly interconverted by external stimuli that utilize host-guest and metal-ligand
Dinuclear PdII/PtIIcomplexes [M2(phosphine)n(thio-ligand)3]Cl incorporating N,S-bridged pyridine-2-thiolate and benzimidazoline-2-thiolate
Lobana, Tarlok S.,Sandhu, Amanpreet K.,Mahajan, Rakesh K.,Hundal, Geeta,Gupta, Sushil K.,Butcher, Ray J.,Castineiras, Alfonso
, p. 25 - 35 (2017)
Equimolar reaction of [PdCl2(dppm)] {dppm?=?bis(diphenylphosphino) methane} with pyridine-2-thione (pySH) in presence of NaOH base in aqueous ethanol formed dinuclear mixed-ligand complex, [PdII2(μ-κ2:N,S-pyS)3(μ-P,P-dppm)]Cl 1. Similarly, reaction of PdCl2(PPh3)2with benzimidazoline-2-thione (bzimSH) in 1:2?M ratio in the presence of Et3N base in acetonitrile has formed a dinuclear complex, [PdII2(μ-κ2:N,S-bzimS)2(κ1-S-bzimS)(PPh3)3]Cl·2H2O 2. Surprisingly, analogous thio-ligand, 1,3-imidazoline-2-thione (imzSH), merely formed a simple square planar complex, [Pd(κ1-S-imzSH)4]Cl2·2H2O 3. The reaction of H2PtCl6with pySH and dppm (1:1:1?M ratio) in the presence of Et3N base in toluene–ethanol (1:1:: v/v) mixture also formed a mixed-ligand dinuclear complex [PtII2(μ-κ2:N,S-pyS)3(μ-P,P-dppm)]Cl similar to 1. All these complexes have been characterized using analytical data, IR, NMR (1H,31P), UV–vis, fluorescence, ESI-mass and single crystal X-ray crystallographic techniques. The anionic thio-ligands are N,S-bridged in complexes 1 and 4, both N,S-bridged and κ1-S bonded in 2 and as neutral κ1-S bonded in 3. There are short M?M contacts in 1 and 4 (1: 2.7249(5) ? 4: 2.7350(8) ?). Complexes 1, 3 and 4 showed intense fluorescence. ESI mass spectral studies of 1, 3 and 4 revealed the formation of molecular ions and other species.
Schiff base triphenylphosphine palladium (II) complexes: Synthesis, structural elucidation, electrochemical and biological evaluation
Shabbir, Muhammad,Akhter, Zareen,Ahmad, Iqbal,Ahmed, Safeer,Shafiq, Maryam,Mirza, Bushra,McKee, Vickie,Munawar, Khurram Shahzad,Ashraf, Ahmad Raza
, p. 250 - 258 (2016)
The complexes N-(2-oxidophenyl)salicylideneiminatotriphenylphosphine palladium(II) (1) and N-(2-sulfidophenyl)salicylideneiminato triphenylphosphine palladium(II) (2) of tridentate Schiff bases derived from salicylaldehyde and an amino- or thiophenol, have been synthesized and characterized by various spectroscopic, analytical and electro-analytical techniques. X-ray single crystal analysis of complex 1 has revealed its square planar geometry. The thermal analysis has shown the absence of coordinated water and final degradation product is PdO. The alkaline phosphatase studies have indicated that enzymatic activity is concentration dependent which is inversely proportional to the concentration of the compounds. The biological assays (brine shrimp cytotoxicity, DPPH) have reflected their biologically active and mild antioxidant nature. However, results of DNA protection assay have shown that they possess moderate protective activity against hydroxyl free radicals (OH). The voltammetric studies ascertain two-electron reduction of the compounds through purely diffusion controlled process and reveal intercalative mode of drug DNA interactions.
Gaunt, J. C.,Shaw, B. L.
, p. 511 - 516 (1975)
Palladium catalyzed hydrodechlorination of α-chloroacetophenones by hydrogen transfer from the H2O-CO system
Cavinato,Pasqualetto,Ronchin,Toniolo
, p. 15 - 22 (1997)
PdCl2(PPh3)2, in combination with an extra amount of PPh3, is an excellent catalyst precursor for the hydrodechlorination of α-chloroacetophenone to acetophenone by hydrogen transfer from the H2O-CO system. The reaction occurs with concomitant evolution of CO2. Under typical reaction conditions (50-70°C, 40-80 atm, substrate/Pd/P = 2000/1/50, H2O/substrate = 8-12/1), the reaction occurs in 70-80% yield in 2 h, using ethanol or dioxane as a solvent ([Pd] = 5.10-4 mol · l-1). When the catalyst precursor is employed without adding an additional amount of PPh3 extensive decomposition to metallic palladium occurs. Also Pd/C is active in promoting the hydrodechlorination reaction. As expected the reaction rate increases upon increasing concentration of catalyst, carbon monoxide pressure and temperature. The yield is slightly influenced by the concentration of the substrate. The effect of the concentration of H2O is the most significant. In ethanol as a solvent at low concentration of water the reaction rate increases to reach a plateau above 6-7 10-2 mol · l-1 of water. On the basis of the fact that it is known that (i) the precursor is reduced to a Pd(0) species by the H2O-CO system, even in the presence of hydrochloric acid, which is freed during the course of the hydrodechlorination reaction and that (ii) the starting α-chloroacetophenone oxidatively adds to Pd(0) to give Pd(CH2COPh)Cl(PPh3)2 (I) and that (iii) this complex reacts with hydrochloric acid to give acetophenone and PdC12(PPh3)2 (II), it is proposed thai the hydrodechlorination reaction proceeds via the intermediacy of a species analogous to complex (I) and that (II) is reduced to the Pd(0) complex through the intercation of CO and H2O with the metal center to give a species having a Pd-(COOH) moiety, which after β-hydride abstraction gives a palladium-hydride species with concomitant evolution of CO2. The hydride gives off a proton and reduces Pd(II) returning a Pd(0) species back to the catalytic cycle. We found also that complex (I) is reduced to a Pd(0) complex with formation of acetophenone through the action of H2O and CO. It is proposed that this reaction, which may be at the base of a different catalytic path, occurs via the intermediacy of a species having a H-Pd-(CH2COPh) which, after reductive elimination of acetophenone give the Pd(0) complex starting a new catalytic cycle. In the case of the Pd/C catalyzed hydrodechlorination it is suggested that H2O and CO interacts on the surface of the metal to give a hydride and evolution of CO2 and that this hydride displaces a chloride anion from α-chloroacetophenone absorbed on the catalytic surface to give the hydrodechlorination product.
UNUSUAL REARRANGEMENT OF ?-VINYLPALLADIUM COMPLEXES INTO η2-OLEFIN COMPLEXES. THE STRUCTURE OF (η2-1-TRIPHENYLPHOSPHONIUM-2-CARBOMETHOXYETHYLENE)-(TRIPHENYLPHOSPHINE)IODOPALLADATE
Rybin, L. V.,Petrovskaya, E. A.,Rubinskaya, M. I.,Kuz'mina, L. G.,Struchkov, Yu.T.,et al.
, p. 119 - 130 (1985)
β-Substituted ?-vinylpalladium complexes (I) (X = Cl, I; R = Me, Et) have been obtained by interaction of the E- and Z-β-halogen acrylates with tetrakis(triphenylphosphine)palladium.On heating complexes I rearrange into isomeric η2-olefin-ylidepalladium complexes (II).The structure of these complexes has been established by X-ray study of the compound with X = I, R = Me.
Convergent synthesis of alkynylbis(bidentate phosphine)ruthenium dendrimers
McDonagh, Andrew M.,Powell, Clem E.,Morrall, Joseph P.,Cifuentes, Marie P.,Humphrey, Mark G.
, p. 1402 - 1413 (2003)
The convergent synthesis of alkynylbis(bidentate phosphine)ruthenium dendrimers was discussed. The nonlinear optical (NLO) properties of alkynylmetal complexes were also examined. It was demonstrated that electron-rich organometallic dendrimers with metals dispersed through the dendritic structures were synthetically accessible.
REDOX TROPONIZATION OF 4-METHYL-4-DIBROMOMETHYL-2,5-CYCLOHEXADIEN-1-ONE BY HTE ACTION OF Pd(PPh3)4
Nikanorov, V. A.,Gavrilova, G. V.,Rozenberg, V. I.,Reutov, O. A.
, (1987)
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Moynahan, E. B.,Popp, F. D.,Werneke, M. F.
, p. 229 - 232 (1969)
Charge-Assisted phosph(v)azane anion receptors
Bond, Andrew D.,Goodman, Jonathan M.,Lee, Sanha,Plajer, Alex J.,Wright, Dominic S.
, p. 3403 - 3407 (2020)
Coordination of Cu(i) or Pd(ii) to seleno-cyclodiphosph(v)azanes of the type [RNH(Se)P(μ-NtBu)]2 results in positively charged anion receptor units which have increased anion affinity over the neutral seleno-phosph(v)azanes, due to the increase in electrostatic interactions between the receptor and the guest anions. The same effect is produced by replacement of one of the PSe units by a P-Me+ unit.
Erratum: Oxidative addition of Sn-C bonds on palladium(0): Identification of palladium-stannyl species and a facile synthetic route to diphosphinostannylene-palladium complexes (Organometallics (2010) 29:22 5904-5911. DOI: 10.1021/om1007067)
Derrah, Eric J.,Warsink, Stefan,De Pater, Jeroen J. M.,Cabon, Yves,Reboule, Irena,Lutz, Martin,Klein Gebbink, Robertus J. M.,Deelman, Berth-Jan
, p. 2914 - 2918 (2014)
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Synthesis of a diferrocenylvinylidene complex by migration of a ferrocenyl substituent
Korb, Marcus,Moggach, Stephen A.,Low, Paul J.
supporting information, p. 4251 - 4254 (2021/05/05)
An unusual 1,2-ferrocenyl migration has been observed following reactions of [Ru(dppe)Cp][BArF4] with diferrocenylacetylene, extending the scope of group rearrangments beyond methyl (Wagner-Meerwein) and phenyl entities. Ferrocene-containing bis(alkynes) RCCArCCR (R = Fc, Ar = 1,4-phenylene; R = Ph, Ar = 1,1′-ferrocenylene) gave bimetallic bis(vinylidene) complexes following two consecutive rearrangements.
Epoxyanthracene Derivatives and Dicarbonylation on Benzene Ring via Hexadehydro-Diels-Alder (HDDA) Derived Benzynes with Oxazoles
Hu, Qiong,Hu, Yimin,Lei, Yu,Yang, Feihu,Zheng, Xiaojie,Zhu, Wenjing
supporting information, (2021/11/22)
A capture reaction of hexadehydro-Diels-Alder (HDDA) derived benzyne with various substituted oxazoles is reported. With methyl, hydrogen, or phenyl as the substituent at 2-position of oxazole, tetraynes afforded epoxyanthracene derivatives or underwent dicarbonylation on benzene ring. The reaction does not require any catalyst or additive. The mechanism behind the reaction was investigated. The obtained polycyclic product structure has potential application value in optoelectronic materials. The availability of dicarbonylated arene implies the uniqueness of HDDA benzyne reaction compared with traditional benzyne.
