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51.
Kinetic studies of cyanide exchange on [M(CN)(4)](2-) square-planar complexes (M = Pt, Pd, and Ni) were performed as a function of pH by (13)C NMR. The [Pt(CN)(4)](2-) complex has a purely second-order rate law, with CN(-) as acting as the nucleophile, with the following kinetic parameters: (k(2)(Pt,CN))(298) = 11 +/- 1 s(-1) mol(-1) kg, DeltaH(2) (Pt,CN) = 25.1 +/- 1 kJ mol(-1), DeltaS(2) (Pt,CN) = -142 +/- 4 J mol(-1) K(-1), and DeltaV(2) (Pt,CN) = -27 +/- 2 cm(3) mol(-1). The Pd(II) metal center has the same behavior down to pH 6. The kinetic parameters are as follows: (k(2)(Pd,CN))(298) = 82 +/- 2 s(-1) mol(-1) kg, DeltaH(2) (Pd,CN) = 23.5 +/- 1 kJ mol(-1), DeltaS(2) (Pd,CN) = -129 +/- 5 J mol(-1) K(-1), and DeltaV(2) (Pd,CN) = -22 +/- 2 cm(3) mol(-1). At low pH, the tetracyanopalladate is protonated (pK(a)(Pd(4,H)) = 3.0 +/- 0.3) to form [Pd(CN)(3)HCN](-). The rate law of the cyanide exchange on the protonated complex is also purely second order, with (k(2)(PdH,CN))(298) = (4.5 +/- 1.3) x 10(3) s(-1) mol(-1) kg. [Ni(CN)(4)](2-) is involved in various equilibrium reactions, such as the formation of [Ni(CN)(5)](3-), [Ni(CN)(3)HCN](-), and [Ni(CN)(2)(HCN)(2)] complexes. Our (13)C NMR measurements have allowed us to determine that the rate constant leading to the formation of [Ni(CN)(5)](3-) is k(2)(Ni(4),CN) = (2.3 +/- 0.1) x 10(6) s(-1) mol(-1) kg when the following activation parameters are used: DeltaH(2)() (Ni,CN) = 21.6 +/- 1 kJ mol(-1), DeltaS(2) (Ni,CN) = -51 +/- 7 J mol(-1) K(-1), and DeltaV(2) (Ni,CN) = -19 +/- 2 cm(3) mol(-1). The rate constant of the back reaction is k(-2)(Ni(4),CN) = 14 x 10(6) s(-1). The rate law pertaining to [Ni(CN)(2)(HCN)(2)] was found to be second order at pH 3.8, and the value of the rate constant is (k(2)(Ni(4,2H),CN))(298) = (63 +/- 15) x10(6) s(-1) mol(-1) kg when DeltaH(2) (Ni(4,2H),CN) = 47.3 +/- 1 kJ mol(-1), DeltaS(2) (Ni(4,2H),CN) = 63 +/- 3 J mol(-1) K(-1), and DeltaV(2) (Ni(4,2H),CN) = - 6 +/- 1 cm(3) mol(-1). The cyanide-exchange rate constant on [M(CN)(4)](2-) for Pt, Pd, and Ni increases in a 1:7:200 000 ratio. This trend is modified at low pH, and the palladium becomes 400 times more reactive than the platinum because of the formation of [Pd(CN)(3)HCN](-). For all cyanide exchanges on tetracyano complexes (A mechanism) and on their protonated forms (I/I(a) mechanisms), we have always observed a pure second-order rate law: first order for the complex and first order for CN(-). The nucleophilic attack by HCN or solvation by H(2)O is at least nine or six orders of magnitude slower, respectively than is nucleophilic attack by CN(-) for Pt(II), Pd(II), and Ni(II), respectively. 相似文献
52.
Chatterton N Gateau C Mazzanti M Pécaut J Borel A Helm L Merbach A 《Dalton transactions (Cambridge, England : 2003)》2005,(6):1129-1135
The ligand N,N'-bis[(6-carboxy-2-pyridylmethyl]ethylenediamine-N,N'-diacetic acid (H(4)bpeda) was synthesised using an improved procedure which requires a reduced number of steps and leads to a higher yield with respect to the published procedure. It was obtained in three steps from diethylpyridine-2,6-dicarboxylate and commercially available ethylenediamine-N,N[prime or minute]-diacetic acid with a total yield of approximately 20%. The crystal structure of the hexa-protonated form of the ligand which was determined by X-ray diffraction shows that the four carboxylates and the two amines are protonated. The crystal structure of the polynuclear complex [Gd(bpeda)(H(2)O)(2)](3)[Gd(H(2)O)(6)](2)Cl(3)(2), isolated by slow evaporation of a 1:1 mixture of GdCl(3) and H(4)bpeda at pH approximately 1, was determined by X-ray diffraction. In complex three [Gd(bpeda)(H(2)O)(2)] units, containing a Gd(III) ion ten-coordinated by the octadentate bpeda and two water molecules, are connected in a pentametallic structure by two hexa-aquo Gd(3+) cations through four carboxylato bridges. The protonation constants (pK(a1)= 2.9(1), pK(a2)= 3.5(1), pK(a3)= 5.2(2), and pK(a4)= 8.5(1)) and the stability constants of the complexes formed between Gd(III) and Ca(II) ions and H(4)bpeda (log beta(GdL)= 15.1(3); log beta(CaL)= 9.4(1)) were determined by potentiometric titration. The unexpected decrease in the stability of the gadolinium complex and of the calcium complex of the octadentate ligand bpeda(4-) with respect to the hexadentate ligand edta(4-) has been interpreted in terms of an overall lower contribution to stability of the metal-nitrogen interactions. The EPR spectra display very broad lines (apparent DeltaH(pp) approximately 800-1200 G at X-band and 90-110 G at Q-band depending on the temperature), indicating a rapid transverse electron spin relaxation. At X-band, Gd(bpeda) is among the fastest relaxing Gd(3+) complexes to date suggesting that the presence of pyridinecarboxylate chelating groups in itself does not lead to slow electron relaxation. 相似文献
53.
Zusammenfassung Es werden molekulare Struktur, Energie des Grundzustandes, Bindungsabstände, Bindungsenergie, Ionisierungsenergie und Protonenaffinität der Siliziumwasserstoffverbindungen SiH
n
, SiH
n
+ und SiHn
– (n=3, 4 oder 5) nach der Einzentrenmethode berechnet.
OCE-calculations on some silicon hydrides of the type SiH n , SiH n + and SiH n –
OCE-Calculations are reported for molecular structures, ground state energies, bond distances, binding energies, ionization potentials and proton affinities of the silicon hydrides SiH n , SiH n + and SiH n – (n=3, 4 or 5).
Résumé Calcul par la méthode monocentrique de la structure moléculaire, de l'énergie de l'état fondamental, des longueurs de liaison, des énergies de liaison, des potentiels d'ionisation et des affinités protoniques pour les hydrures de silicium SiH n , SiH n + et SiH n – (n=3, 4 ou 5).相似文献
54.
An extremely sensitive, reliable and simple procedure is described for the determination of physiological palladium, platinum and gold in human urine. The urine samples were adjusted to pH 4 (Pd, Au) or pH 5 (Pt), followed by conversion of the analytes to their pyrrolidinedithiocarbamate complexes. These complexes were separated from the matrix by liquid-liquid extraction into 4-methyl-2-pentanone resulting in a 25-fold enrichment. Determination was by electrothermal atomic absorption spectrometry (ET-AAS) using longitudinal inverse alternating current Zeeman-effect background correction. The limits of detection calculated from three standard deviations of the blank values were 20 ng l−1 for Pd and Au and 70 ng l−1 Pt. Within-day precision (n = 10, 5 μg l−1) ranged 5.2%–7.7%. The procedure is successfully applied to determine urinary palladium, platinum and gold in nine unexposed persons. Palladium levels in urine ranged < 20–80 ng l−1 (arithmetical MEAN=38.7 ng l−1), while gold levels ranged < 20–130 ng l−1 (36.0 ng l−1). Physiological platinum levels in urine were all < 70 ng l−1. The accuracy of the procedure was checked by analyzing a series of urine samples by a second independent method (magnetic sector field inductively-coupled plasma-mass spectrometry) in combination with UV photolysis. 相似文献
55.
The structural parameters of the completely relaxed 4–21G ab initio geometries of more than 30 basic organic compounds are compared to experimental results. Some ranges for systematic empirical corrections, which relate 4–21G bond distances to experimental parameters, are associated with total energy increments. In general, for the currently feasible comparisons, the following corrections can be given which relate calculated distances to experimental rg parameters and calculated angles to rs-structures For CC single bond distances, deviations between calculated and observed parameters (rg) are in the ranges of ?0.006(2) to ?0.010(2) Å for normal or unstrained hydrocarbons; ?0.011(3) to ?0.016(3) Å for cyclobutane type compounds; and +0.001(5) to +0.004(4) Å for CH3 conjugated with CO. For CO single bonds the ranges are ?0.006(9) to +0.002(3) Å for CO conjugated with CO; and ?0.019(3) to ?0.027(9) Å for aliphatic and ether compounds. A very large and exceptional discrepancy exists for the highly strained ethylene oxide, rs — re = ?0.049(5) Å and in CH3OCH3 and C2H5OCH3 the rs — re differences are ?0.029(5), ?0.040(10) and ?0.025(10) Å. Some of these discrepancies may also be due to deficiencies of the microwave substitution method caused by atomic coordinates close to inertial planes. For CN bonds, two types of NCH3 corrections are from +0.005(6) to ?0.006(6) and from ?0.009(2) to ?0.014(6) Å; and the range for NCO is +0.012(3) to +0.028(4) Å. For isolated CC double bonds the range is + 0.025(2) to +0.028(2) Å. For conjugated CC double bonds the correction is less positive (+0.014(1) Å for benzene). For CO double bonds the corrections are ?0.004(3) to +0.003(3) Å. For bond angles of type HCH, CCH, CCC, CCO, CCO, OCO, NCO and CCC the corrections are of the order of magnitude about 1–2° (or better). Angles centered at heteroatoms are less accurate than that, when hydrogen atoms are involved. Differences in HOC and NHC angles were found in a range of ?2.3(5)° to ?6.2(4)°. 相似文献
56.
The electron-diffraction data for cyclohexane and perdeuterated cyclohexane were analyzed and the results were compared. It was found that rg(C-C) = 1.535 Å (±0.002) for both compounds; rg (C-H) = 1.116 Å (±0.004) and rg(C-D) = 1.109 Å (±0.003). Observed hydrogen isotope effects in mean amplitudes agree very well with calculated ones. The C-C bond distance of cyclohexane is in good agreement with some of the previous studies, which is of importance in view of a recent scaling controversy involving this parameter. 相似文献
57.
The structure of [(CF3N2NMe)Mo(CH2SiMe3)2] (in which (CF3N2NMe)2? is [(3‐CF3C6H4NCH2CH2)2NMe]2?) is approximately trigonal bipyramidal with one axial and one equatorial alkyl ligand. Heating of solutions of [(CF3N2NMe)Mo(CH2SiMe3)2] in [D6]benzene in the presence of five equivalents of 2‐butyne led to diamagnetic [(CF3N2NMe)Mo(CHSiMe3)(η2‐MeC?CMe)], whose structure is approximately square pyramidal with the alkyne occupying the axial site. Addition of one equivalent of cyclohexene sulfide to [(CF3N2NMe)Mo(CH2SiMe3)2] at room temperature produced the diamagnetic, dimeric molybdenum(IV) sulfido complex, [{(CF3N2NMe)MoS}2]. This complex is composed of two approximately trigonal bipyramidal centers, each containing one axial and one equatorial sulfur atom. Oxidation of [(CF3N2NMe)Mo(CH2SiMe3)2] with hexachloroethane resulted in formation of tetramethylsilane, HCl, and the sparingly soluble, red alkylidyne complex, [{(CF3N2NMe)Mo(CSiMe3)Cl}2]. This complex forms a dimer through bridging chlorides. The oxidation reactions of [(CF3N2NMe)Mo(CH2SiMe3)2] with 2‐butyne, cyclohexene sulfide, or C2Cl6 are all proposed to proceed by α‐hydrogen abstraction in the MoVI species to yield (initially) the Mo?CHSiMe3 species and tetramethylsilane. 相似文献
58.
Solutions of the perfluoro anion-exchange membrane TosHex® in a solvent mixture composed of methanol + isopropanol + water (1:1:1) were prepared and applied in coating glassy carbon electrodes. The evaporated films were used to accumulate the Fe(CN)
6 redox couple on the electrode surface. The magnitude of the electrochemical response of the loaded films is comparable with that for Nafion® incorporated cationic redox species. The multicharged Fe(CN)
6 couple accumulated in Tosflex® film causes an ion cross-linking of the polymeric backbone, thus decreasing ion transport in the film substantially. 相似文献
59.
60.
Shuhui Yu Kui Yao Francis Eng Hock Tay 《Journal of Sol-Gel Science and Technology》2007,42(3):357-364
The preferential formation of a pyrochlore structure is a knotty problem in the preparation of Pb(Zn1/3Nb2/3)O3 (PZN)-based thin film materials and its presence is significantly detrimental to the dielectric and piezoelectric properties.
In this study, 40 mol% of PZN was replaced with Pb(Mg1/3Nb2/3)O3 (PMN) for obtaining a perovskite composition around a morphotropic phase boundary (MPB), (1−x)(0.6PZN-0.4PMN)-xPT ((1−x)PZMN-xPT, PT: PbTiO3) where x = 0.23. The thin films with this composition were prepared with a polyethylene glycol (PEG) modi-fied sol-gel method on LaAlO3 substrates. The microstructural evolution of the films on heat treatment was examined with X-ray diffraction. With the aid
of PEG, the formation of the pyrochlore phase was suppressed and the perovskite phase formed directly from the amorphous gel
film. The multilayer films with a thickness around 0.25 μm showed a single perovskite phase without any detectable pyrochlore
structure. Microscopic images showed uniform grain size of a few tens of nanometers. The role of the polymer dramatically
promoting the perovskite phase was investigated with the aid of X-ray photoelectron spectroscopy and thermal analysis. The
dielectric constant of the obtained film was 4160 at 1 kHz. The film demonstrated typical ferroelectric hysteresis loops and
exhibited excellent piezoelectric performance. 相似文献