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We investigated the self-assembly process of a Pd4L8 double-walled square (DWS) from [PdPy*4]2+ (Py*: 3-chloropyridine used as the leaving ligand on the PdII center) and an organic ditopic ligand by QASAP (quantitative analysis of self-assembly process). DWS is assembled mainly through three pathways. Within 5 minutes of the self-assembly, all of the substrates, the metal source and the organic ditopic ligand, were completely consumed and converted into primary intermediates. In 2 h, the primary intermediates afforded 30 % of DWS, 200-nm-sized large intermediates, and a relatively stable transient intermediate. This stable intermediate was characterized as a kinetically trapped Pd3L6 double-walled triangle (DWT) by NMR and mass measurements. From 2 h to 1 day, 19 % of DWS was formed from the 200-nm-sized large intermediate with the aid of Py*, which is not a component of the final assembly. After 1 day, the remaining large intermediate and DWT afforded 39 % of DWS with the aid of Py* again. This self-assembly process is quite different from that of previously reported single-walled macrocycles, and the change in the self-assembly pathway would arise from the difference in the flexibility of ditopic ligands. This study revealed a complicated multiplicity, not a simple single pathway, of the self-assembly process of DWS.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A series of new complexes incorporating the functionalized tetrathiafulvalene (TTF) ligands ortho-(CH3)2(P(C6H5) 2)2-TTF (o-P2) and (P(C6H5)2)4 TTF (P4) have been prepared and studied by fast atom bombardment mass spectrometry (FABMS). The mononuclear o-P2 complexes [M(o-P2)2](BF4)2 (M = Fe, Pd, Pt) and [Co(o-P2)2(NCCH3)2](BF4)2 were synthesized from reactions of the free ligand with the fully solvated BF4- salts [M(NCCH3)n](BF4)2 (M = Fe, Co, n = 6; M = Pd, Pt, n = 4). The dinuclear P4 complex, [Pt2(P4)(NCCH3](BF4)4, was produced by reacting the free ligand with PtCl2(NC7H5)2followed by abstraction of the chlorides with AgBF4 in acetonitrile. Reaction of [Pd(NCCH3)](BF4)2 with 1 equiv of P4 produces the polynuclear compound formulated as [Pd(P4)]n(BF4)2n which was characterized by infrared, 1H, and 31P{1H} NMR spectroscopies and elemental analysis. The use of FABMS in this study was undertaken in order to elucidate the chemical options of multiply charged cations in the desorption process from the liquid matrix to the gas phase. The use of additives to the FAB matrix (m-nitrobenzyl alcohol) was demonstrated for the P4 complexes which do not give spectra in this medium due to a high positive net charge. The addition of triflic acid (HOTf or CF3SO3H) to the FAB matrix/analyte solution was shown to assist in the MS analysis of cationic complexes with up to six charges and a mass range up to m/z 4000. When HOTf is added, bound OTf- anions are formed and are attached to the cationic complex, lowering the net charge to +1. The method of using matrix additives as opposed to chemically synthesizing the OTf- compounds is a convenient in situ method which produces species that are capable of being analyzed by FABMS.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The complexes M(PNP)22+ (M = Pd, Pt, PNP = Et2PCH2N(Me)CH2PEt2) were synthesized by addition of PNP to Pd(CH3CN)4(BF4)2 and (COD)PtCl2, respectively. Pd(PNP)2 was synthesized by reaction of Pd(PNP)22+ with H2 and tetramethylguanidine (TMG) in CH3-CN. The thermodynamic hydride donor ability, DeltaGH-, for HPt(PNP)2+ (54.7 kcal/mol) was measured by heterolytic cleavage of hydrogen in the presence of NEt3 in CH3CN. The hydride donor ability of HPd(PNP)2+ (51.1 kcal/mol) was determined by measuring the equilibrium constant for direct hydride transfer to Pt(PNP)22+. The M(II) complexes undergo reversible, two-electron reductions in benzonitrile. The measured reduction potentials were used in a thermodynamic cycle to estimate pKa values of 22.1 and 27.6 for deprotonation of HPd-(PNP)2+ and HPt(PNP)2+, respectively. The palladium hydride has an acidity equal to that of the nickel hydride and is a better hydride donor than both the nickel and platinum analogues. This shows that it is possible for transition metal hydrides to act simultaneously as both acids and hydride donors.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A phosphine sulfide Pd(II) complex, [Pd(p2S2)2](BF4)2 (1) (p2S2 = 1,2-bis(diphenylphosphino)ethane disulfide), was synthesized and characterized by an X-ray crystal structure analysis and 31P NMR spectroscopy. The p2S2 ligand exchange rate of 1 with free p2S2 in chloroform was revealed to be comparable to the general solvent exchange rate on Pd(II). The catalytic activity of 1 was evaluated by carrying out the Heck reaction. The diminishing of the induction period and acceleration of the reaction were observed for 1 by comparing the phosphine Pd(II) complexes with a leaving chloro ligand, [PdCl(p3)]Cl (p3 = bis[2-(diphenylphosphino)ethyl]phenylphosphine) and [PdCl(pp3)]Cl (pp3 = tris[2-(diphenylphosphino)ethyl]phosphine), and the catalytic activity was comparable to that of the phosphine Pd(0) complex, [Pd(PPh3)4]. Such a high catalytic activity of 1 is attributed to the pi-accepting ability of the phosphine sulfide S atom which stabilizes the catalytically active Pd(0) species electronically and weak sigma-donation of the S atom which does not block the formation and a subsequent reaction of the Pd(II) substrate adduct in the catalytic cycle.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Electric Literature of 21797-13-7, The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.21797-13-7, Name is Tetrakis(acetonitrile)palladium(II) tetrafluoroborate, molecular formula is C8H12B2F8N4Pd. In a Article,once mentioned of 21797-13-7

Ligand exchange at square-planar [Pd(MeCN)4]2+ and [Pd(EtCN)4]2+ has been studied by 1H NMR line broadening and at [Pt(MeCN)4]2+ and [Pt(EtCN)4]2+ by isotopic labelling using 1H NMR spectroscopy in deuteriated nitromethane. Exchange takes place via two-term rate laws Rex/4 = (k1 + k2[RCN])cM with well defined k1 paths. Rate constants per co-ordination site k1298/s-1, k2298/kg mol-1 s-1 are 6.9 ± 1.6, 34 ± 3; 0.59 ± 0.12, 34 ± 3; 10.7 ± 1.8, 35 ± 4; (5.1 ± 2.3) × 10-6, (2.8 ± 0.2) × 10-5 and (5.5 ± 1.0) × 10-6, (3.3 ± 0.2) × 10-5 for [Pd(MeCN)4][CF3SO3]2, [Pd(MeCN)4][BF4]2, [Pd(EtCN)4][CF3SO3]2, [Pt(MeCN)4][CF3SO3]2 and [Pt(EtCN)4]-[CF3SO3]2, respectively. For [Pd(MeCN)4]2+ the k1 path is much larger for triflate than for tetrafluoroborate as counter ion. Changing the tetrafluoroborate concentration has no effect on the exchange rate of acetonitrile at [Pd(MeCN)4]2+. In this case the k1 path is ascribed to an attack by solvent at the metal centre. For triflate saturation kinetics is observed. This can be rationalized in terms of ion-pair formation followed by reversible intramolecular exchange of nitrile for triflate within the ion pair, with an equilibrium constant Kip300 = 8 ± 2 kg mol-1 and a rate constant k300 = 12.5 ± 1.3 s-1. All activation entropies are negative, indicating associative activation. A new, simple one-step synthesis of the substrate complexes as their triflate salts, using [M(acac)2] (acac = acetylacetonate) as starting material, and of [Pd(MeCN)4][BF4]2 using palladium(II) acetate, is described.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Electric Literature of 21797-13-7, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.21797-13-7, Name is Tetrakis(acetonitrile)palladium(II) tetrafluoroborate, molecular formula is C8H12B2F8N4Pd. In a article,once mentioned of 21797-13-7

The new bifunctional ligands Ph2PCH=CPh[OP(O)(OR)2] (1) (1a, R = Et; 1b, R = Ph) represent the first examples of P,O derivatives resulting from the association of a phosphine moiety and an enolphosphate group. The Z stereochemistry about the double bond provides a favorable situation for these ligands to act as P,O-chelates. Neutral and cationic Pd(II) complexes have been synthesized and characterized, in which 1a or 1b acts either as a P-monodentate ligand or a P,O-chelate, via coordination of the oxygen atom of the P=O group. In the latter case, it has been observed that phosphines 1a and 1b can display a hemilabile behavior, owing to successive dissociation and recoordination of the O atom. Competition experiments revealed that phosphine 1a presents a higher chelating ability than 1b, a feature ascribed to the more electrodonating properties of the ethoxy groups in 1a compared to the phenoxy groups in 1b. P,O-Chelation affords seven-membered metallocycles, which is unusual for P,O-chelates. Complexes trans-[PdCl2{Ph 2PCH=C(Ph)OP(O)(OPh)2}2] (2b), [PdCl{Ph 2PCH=C(Ph)OP(O)(OEt)2}(mu-Cl)]2 (3a), [Pd(dmba){Ph2PCH=C(Ph)OP(O)(OEt)2}][PF6] (8a?), and cis-[Pd{Ph2PCH=C(Ph)OP(O)OEt)2}][BF 4]2 (10a) have been structurally characterized. Interestingly, the seven-membered rings in 8a? and 10a adopt a sofa conformation with the double bond lying almost perpendicular to the plane containing the Pd, the two P, and the two O atoms.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

23-Sep-2021 News Archives for Chemistry Experiments of 21797-13-7

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Room for one more? The structures of nanosized Pd52 and Pd 66 clusters that are based upon a common Pd38 vertex-truncated nu-octahedral kernel have been determined. The 45 CO ligands in the Pd66 cluster (see core structure), [Pd66(CO) 45-(PEt3)16], are described in terms of one extra and 44 normal ligands, two of which undergo rearrangement to accommodate the 45th CO ligand without causing any substantial changes to the architecture of the metal core. (Figure Presented)

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A synthesis for a series of tetrapodal nitrogen ligands (N,N?-dibenzyl-N,N?-di(quinoline-2-methyl)-1,2-ethylene diamine (DBQED, 1), N,N?-dimethyl-N,N?-di(quinoline-2-methyl)-1,2-ethylene diamine (DMQED, 2), (1R,2R)-(-)-N,N?-di(quinoline-2-methylene) diiminocyclohexane (DQEDC, 3), N,N?-di(quinoline-2-methylene)-1,2-phenylene diimine (DQPD, 4) and for their corresponding neutral and cationic palladium(II) complexes of the types [(1,2,4)PdCl2] (5a, 6a, 7) and [(1,2,3,4)Pd(NCCH3)x](Y)2 (5b, 5c, 6b, 6c, 8, 9), x=0, 2; Y=BF4-, NO3- is reported. The dicationic palladium(II) complex [Pd(DBQED)(NO3)2·H2O] (5c) crystallizes in the monoclinic space groups P21/c (no. 14) with a=11.458(1), b=15.302(1) A, c=20.644(2) A, beta=99.23(1) and V=3572.7 A3, Z=4. All four nitrogen donors are attached to the Pd(II)-center in the chiral and C2-symmetric complex 5c. The two quinoline nitrogen atoms of the more rigid Schiff bases (DQEDC, 3; DQPD, 4) do not coordinate coincidentally to Pd(II). A fluxional coordination behavior is suggested for these quinoline donors, which enables this new complex family to act as catalysts for norbornene polymerization, even when chloride is present as a counter ion. Introduction of an enantiomerically pure trans-1,2-cyclohexyl bridge into the Schiff base ligand systems afforded the formation of partially stereoregular polynorbornene.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Application of 21797-13-7, Chemistry is the science of change. But why do chemical reactions take place? Why do chemicals react with each other? The answer is in thermodynamics and kinetics.In a document type is Article, and a compound is mentioned, 21797-13-7, Tetrakis(acetonitrile)palladium(II) tetrafluoroborate, introducing its new discovery.

The compound [Pd(1,4-thioxane)4](BF4)2·4CH 3NO2 crystallizes in the monoclinic space group P21/c with a=9.474(2), b=9.529(5), c=21.945(9) A, beta=99.77(3), Z=2; final R=0.051 for 4325 observed reflections (Pd, C, S and O anisotropically refined). The thioxane ligands around Pd form a square-planar arrangement, with two nitromethane molecules at a distance of 3.115(2) A occupying sites perpendicular to the square-plane formed by the sulfur-bonding thioxanes giving an overall tetragonal bipyramidal coordination around Pd. Intermolecular exchange of 1,4-thioxane on [Pd(1,4-thioxane)4](BF4)2 in deuterated nitromethane and intramolecular interconversion in the bound ligand have been studied as a function of temperature and pressure by 1H NMR lineshape analysis. The first-order rate constant and activation parameters obtained for the intramolecular process, assigned to sulfur inversion, are as follows: ki298=294±26 s-1, DeltaHi?=61.9±1.9 kJ mol-1, DeltaSi?=+10.2±6.5 J K-1 mol-1, DeltaVi?=+2.7±0.2 cm3 mol-1. The intermolecular process yielded the following second-order rate constant and activation parameters: k2298=920±40 m-1 s-1, DeltaH2?=39.5±0.9 kJ mol-1, DeltaS2?=-55.6±2.8 J K-1 mol-1, DeltaV2?=-9.5±0.3 cm3 mol-1. Second-order kinetics and negative values for the entropy and volume of activation indicate an associative Ia or A exchange mechanism. The reactivity of the analogous Pt2+ compound is estimated using the proposed empirical linear correlation function DeltaG?(Pt)=-32.1+1.92DeltaG?(Pd). The calculated second-order rate constant and free energy of activation are 0.3 m-1 s-1 and 76 kJ mol-1, respectively. This relationship indicates also that the well established reactivity order Pd2+?Pt2+ could be reversed for better pi-accepting ligands than MeNC and that, in this case, five-coordinated species on Pt(II) are more stable than the Pd(II) analogue.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Reference of 21797-13-7, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 21797-13-7, molcular formula is C8H12B2F8N4Pd, introducing its new discovery.

TWIM peaks: A macrocycle containing 12 PdII terpyridyl centers was assembled using 4,4?-bipyridyl ligands and characterized by NMR and traveling wave ion mobility mass spectrometry (TWIM-MS). The macrocyclic architecture was also examined by tandem mass spectrometry and collisionally activated dissociation (CAD) experiments (see picture; C gray, N blue, Pd orange), and the resulting fragments were monitored by time-of-flight mass analysis.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method