Purification of xylenol orange by preparative paper chromatography, and examination of its zirconium complex

Preparative paper chromatography is proposed as a suitable method for purification of Xylenol Orange (XO). The last three dissociation constants of pure XO have been determined with the aid of the program SPEKTFOT, the values found being pK(9) = 12.34; pK(8) = 10.66; pK(7) = 6.69 (0.1M KNO(3), 20 +/- 0.5 degrees ). The complexation of zirconium with the purified reagent has been studied and the co-existence of ML and M(2) L complexes proved by use of the program DALSFEK. The following conditional stability constants of the complexes and their molar absorptivities were computed: log beta'(ml) 4.58; log beta'(M(2)L) 11.59; (ML) 2.00 x 10(4); (M(2)L) 9.40x 10(4) l.mole(-1).cm(-1) at 550 nm.     

Molar absorptivities of 2,4-D, cymoxanil, fenpropidin, isoproturon and pyrimethanil in aqueous solution in the near-UV

The absorption spectra of five pesticides, namely 2,4-dichloro-phenoxy acetic acid (2,4-D), cymoxanil, fenpropidin, isoproturon and pyrimethanil, have been measured in aqueous solution using a set-up consisting of two parallel absorption cells coupled to a CCD detector. The absolute values of their molar absorptivity coefficients epsilon were determined in the wavelength-range 240-344 nm with a deuterium-lamp at room temperature (298+/-2 K). Using the Beer-Lambert law, values of epsilon were also determined at 253.7 nm with a Hg-Lamp: epsilon = 145+/-14 for 2,4-D, epsilon = 7940+/-920 for cymoxanil, epsilon = 196+/-14 for fenpropidin, epsilon = 7330+/-880 for isoproturon, epsilon = 13200+/-1400 for pyrimethanil (in units of M(-1) cm(-1)). The quoted errors correspond to 2 sigma obtained from the least square fit analysis and the estimated systematic error of 5% due to the uncertainties in aqueous concentrations. For all the studied compounds, the absorbances measured were lower than 2.3 and did not exhibit any deviation from the Beer-Lambert's law. Our experimental data are discussed and compared to UV spectra of similar molecules when such data were available in the literature. Based on their UV spectra and the calculated fractions of these pesticides in the aqueous phase, their direct photolysis under sunlight environment could occur, except may be for fenpropidin, either in water surfaces or in aqueous droplets contained in the atmospheric clouds.     

The relaxation of OH (v=1) and OD (v=1) by H2O and D2O at temperatures from 251 to 390 K

We report rate coefficients for the relaxation of OH(v=1) and OD(v=1) by H2O and D2O as a function of temperature between 251 and 390 K. All four rate coefficients exhibit a negative dependence on temperature. In Arrhenius form, the rate coefficients for relaxation (in units of 10(-12) cm3 molecule-1 s-1) can be expressed as: for OH(v=1)+H2O between 263 and 390 K: k=(2.4+/-0.9) exp((460+/-115)/T); for OH(v=1)+D2O between 256 and 371 K: k=(0.49+/-0.16) exp((610+/-90)/T); for OD(v=1)+H2O between 251 and 371 K: k=(0.92+/-0.16) exp((485+/-48)/T); for OD(v=1)+D2O between 253 and 366 K: k=(2.57+/-0.09) exp((342+/-10)/T). Rate coefficients at (297+/-1 K) are also reported for the relaxation of OH(v=2) by D2O and the relaxation of OD(v=2) by H2O and D2O. The results are discussed in terms of a mechanism involving the formation of hydrogen-bonded complexes in which intramolecular vibrational energy redistribution can occur at rates competitive with re-dissociation to the initial collision partners in their original vibrational states. New ab initio calculations on the H2O-HO system have been performed which, inter alia, yield vibrational frequencies for all four complexes: H2O-HO, D2O-HO, H2O-DO and D2O-DO. These data are then employed, adapting a formalism due to Troe (J. Troe, J. Chem. Phys., 1977, 66, 4758), in order to estimate the rates of intramolecular energy transfer from the OH (OD) vibration to other modes in the complexes in order to explain the measured relaxation rates-assuming that relaxation proceeds via the hydrogen-bonded complexes.     

Binding of catechols to mononuclear titanium(IV) and to 1- and 5-nm TiO2 nanoparticles

The binding of catechol derivatives (LH 2 = catechol, 4-methyl catechol, 4-t-butyl catechol, and dopamine) to 1- and 4.7-nm TiO2 nanoparticles in aqueous, pH 3.5 suspensions has been characterized by UV-vis spectroscopy. The binding constants derived from Benesi-Hildebrand plots are (2-4) x 10(3) M(-1) for the 1-nm nanoparticles and (0.4-1) x 10(4)M(-1) for the 4.7-nm particles. Ti(IV)L3 complexes were prepared from the same catechols. The L = methyl catechol, and dopamine complexes are reported for the first time. The TiL3 reduction potentials are not very sensitive to the nature of the catechol nor evidently are the binding constants to TiO2 nanoparticles. The intense (epsilon > or = 10(3) M(-1)cm(-1)), about 400-nm, ligand-to-metal charge-transfer (LMCT) absorptions of the nanoparticle complexes are compared with those of the TiL 3 complexes (epsilon approximately 10(4)M(-1) cm(-1)) which lie in the same spectral region. The nanoparticle colors are attributed (as are the colors of the Ti(IV)L3 complexes) to the tails of the about 400-nm LMCT bands.     

Protolytic reactions of 3,3'-dimethylnaphthidine and 3,3'-dimethoxybenzidine

The dissociation constants of diprotonated 3,3'-dimethylnaphthidine (DMN) and 3,3'-dimethoxybenzidine (DMB) have been determined spectrophotometrically. They are: pK(a1) = 2.62 +/- 0.03, pK(a2) = 3.33 +/- 0.09 for DMN: pK(a1) = 2.83 +/- 0.07, pK(a2) = 4.05 +/- 0.12 for DMB. The molar absorptivities (l.mole(-1).cm(-1)) of all forms of the indicators have been also determined: epsilon(B) = 1.68 x 10(4), epsilon(BH(+)) = 9.34 x 10(3), epsilon(BH(2+)(2)) = 1.80 x 10(3) at 300 nm for DMB; epsilon(B) = 7.33 x 10(3), epsilon(BH(+)) = 3.73 x 10(3), epsilon(BH(2+)(2)) = 0 at 330 nm for DMN.     

Formation constants of zinc(II) complexes with Semi-Xylenol Orange

A potentiometric and spectrophotometric investigation on the formation of zinc(II) complexes with Semi-Xylenol Orange (SXO or H(4)L) is reported. In an aqueous solution (mu = 0.1), three 1:1 complex species, MH(2)L, MHL(-), ML(2-), and a 1:2 complex, ML(6-)(2), seem to exist. In a strongly alkaline medium (above pH 12.5) the complexes may dissociate to give zinc hydroxide and L(4-). The formation of a hydroxy complex is not observed. The absorption maxima are at 445 nm (MH(2)L), 466 nm (MHL(-)) and 561 nm (ML(2-)), the molar absorptivities being 2.34 x 10(4), 2.42 x 10(4) and 3.14 x 10(4) 1.mole(-1) .cm(-1) respectively. The formation constants are (at 25 +/- 0.1 degrees ) log K(M)(ML) = 11.84, log K(M)(MHL) = 7.13, log K(M)(MH(2)L) = 2.70, log K(M)(ML(2)) = 16.60.     

Spectral studies on the interaction of yttrium ion with the ligands of phenolic groups: N,N'-Ethylenebis[2-(o-hydroxyphenolic)glycine] and N,N'-di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid

The interactions of yttrium with N,N'-ethylenebis[2-(o-hydroxyphenolic)glycine] (EHPG) and N,N'-di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED) are investigated by using UV difference and fluorescence spectra methods in 0.1M N-2-hydroxyethylpiperazine-N-2-ethanesulfonic acid (Hepes) at pH 7.4. Yttrium binding produces two UV difference peaks near 240 and 294 nm, respectively, that both are the characteristic of phenolic groups binding to yttrium. The molar extinction coefficient of Y-EHPG and Y-HBED are (15.7 +/- 0.40) x 10(3), (15.8 +/- 0.80) x 10(3)cm(-1)M(-1) at 240 nm, respectively. Using EDTA as a competitor the obtained conditional equilibrium constants of the complexes are logK(Y-EHPG) = 15.07 +/- 0.32 and logK(Y-HBED) = 15.18 +/- 0.26, respectively. However, the effects of yttrium binding on the fluorescence intensity of EHPG and HBED are quite different, the former showing a decrease but the latter an increase.     

A high molar extinction coefficient mono-anthracenyl bipyridyl heteroleptic ruthenium(II) complex: synthesis, photophysical and electrochemical properties

In our quest to develop good materials as photosensitizers for photovoltaic dye-sensitized solar cells (DSSCs), cis-dithiocyanato-4-(2,3-dimethylacrylic acid)-2,2'-bipyridyl-4-(9-anthracenyl-(2,3-dimethylacrylic)-2,2'-bipyridyl ruthenium(II) complex, a high molar extinction coefficient charge transfer sensitizer, was designed, synthesized and characterized by spectroscopy and electrochemical techniques. Earlier studies on heteroleptic ruthenium(II) complex analogues containing functionalized oligo-anthracenyl phenanthroline ligands have been reported and documented. Based on a general linear correlation between increase in the length of π-conjugation bond and the molar extinction coefficients, herein, we report the photophysical and electrochemical properties of a Ru(II) bipyridyl complex analogue with a single functionalized anthracenyl unit. Interestingly, the complex shows better broad and intense metal-to ligand charge transfer (MLCT) band absorption with higher molar extinction coefficient (λ(max) = 518 nm, e = 44900 M?1 cm?1), and appreciable photoluminescence spanning the visible region than those containing higher anthracenyl units. It was shown that molar absorption coefficient of the complexes may not be solely depended on the extended π-conjugation but are reduced by molecular aggregation in the molecules.     

NMR diffusion spectroscopy as a measure of host-guest complex association constants and as a probe of complex size

The complexes of cyclohexylacetic acid and cholic acid with beta-cyclodextrin were studied by NMR diffusion coefficient measurements. The diffusion coefficient of the 1:1 cyclohexylacetic acid/beta-cyclodextrin complex, K(a) = 1800 +/- 100 M(-1), is slightly slower (3.23 +/- 0.07 x 10(-6) cm(2) s(-1)) than that of beta-cyclodextrin (3.29 +/- 0.07 x 10(-6) cm(2) s(-1)). The diffusion coefficient of the 1:1 cholic acid/beta-cyclodextrin complex, K(a) = 5900 +/- 800 M(-1), is significantly slower (2.93 +/- 0.07 x 10(-6) cm(2) s(-1)) than that of beta-cyclodextrin. The results indicate that caution should be exercised when studying host-guest complexation by the so-called 'single point' technique. A novel data treatment is introduced which takes into account the diffusion behavior of all of the species when determining K(a). Experimentally determined diffusion coefficients of complexes are also a useful probe of the size of host-guest complexes.     

Analysis and isolation of cationic rhenium(I) and ruthenium(II) multinuclear complexes using size-exclusion chromatography.

Various cationic rhenium(I) and ruthenium(II) mono- and multinuclear complexes were successfully separated by size-exclusion chromatography (SEC), using a 50:50 (v/v) mixture of methanol and acetonitrile with CH3CO2NH4 as an eluent. The logarithms of the molecular weights were accurately linear in the distribution coefficients: for linear-shaped rhenium(I) multinuclear complexes, log M(W) = -2.86K(SEC) + 5.24 (r = -0.990 and n = 15); for ring-shaped rhenium(I) multinuclear complexes, log M(W) = -2.94K(SEC) + 5.40 (r = -0.999; n = 5); for bimetallic complexes including ruthenium(II), log M(W) = -0.40K(SEC) + 3.37 (r = -0.959; n = 6). This separation method is applicable to the preparative-scale separation of cationic multinuclear complexes from a mixture.     

Synthesis and structure investigation of the antibiotic amoxicillin complexes of d-block elements

The study of some transition metals (M) and amoxicillin trihydrate (ACT) ligand complexes (M-ACT) that formed in solution involved the spectrophotometric determination of stoichiometric ratios and their stability constants and these ratios were found to be M:ACT = 1:1, 1:2 and 2:1 in some instances. The calculated stability constants of these chelates, under selected optimum conditions, using molar ratio method have values ranging from K(f) = 10(7) to 10(14). These data were confirmed by calculations of their free energy of formation deltaG, which corresponded to their high stabilities. The separated solid complexes were studied using elemental analyses, IR, reflectance spectra, magnetic measurements, mass spectra and thermal analyses (TGA and DTA). The proposed general formulae of these complexes were found to be ML(H2O)w(H2O)x(OH)y(Cl)2, where M = Fe(II), Co(III), w = 0, x = 2, y = 1, z = 0; M = Co(II), w = 0, x = 1, y = 0, z = 1; M = Fe(III), w = 0, x = 1, y = 2, z = 0; M = Ni(II), Cu(II) and Zn(II), w = 2, x = 0, y = 1, z = 0, where w = water of crystallization, x = coordinated water, y = coordinated OH(-) and z = Cl- in the outer sphere of the complex. The IR spectra show a shift of nu(NH) (2968 cm(-1)) to 2984-2999 cm(-1) of imino group of the ligand ACT and the absence of nu(CO) (beta-lactame) band at 1774 cm(-1) and the appearance of the band at 1605-1523 cm(-1) in all complexes suggest that 6,7-enolization takes place before coordination of the ligand to the metal ions. The bands of M-N (at 625-520 cm(-1)) and of M-O (at 889-7550 cm(-1)) proved the bond of N (of amino and imino groups) and O of C-O group of the ligand to the metal ions. The reflectance spectra and room temperature magnetic measurements refer to octahedral complexes of Fe(II) and Fe(III); square planner form of Co(II), reduced Co(III), Ni(II) and Cu(II)-ACT complexes but tetrahedral form of Zn-ACT complex. The thermal degradation of these complexes is confirmed by their mass spectral fragmentation. These data confirmed the proposed structural and general formulae of these complexes.     

Uptake of organic gas phase species by 1-methylnaphthalene

Organic compounds are a significant component of tropospheric aerosols. In the present study, 1-methylnaphthalene was selected as a surrogate for aromatic hydrocarbons (PAHs) found in tropospheric aerosols. Mass accommodation coefficients (alpha) on 1-methylnaphthalene were determined as a function of temperature (267 K to 298 K) for gas-phase m-xylene, ethylbenzene, butylbenzene, alpha-pinene, gamma-terpinene, p-cymene, and 2-methyl-2-hexanol. The gas uptake studies were performed with droplets maintained under liquid-vapor equilibrium conditions using a droplet train flow reactor. The mass accommodation coefficients for all of the molecules studied in these experiments exhibit negative temperature dependence. The upper and lower values of alpha at 267 and 298 K respectively are as follows: for m-xylene 0.44 +/- 0.05 and 0.26 +/- 0.03; for ethylbenzene 0.37 +/- 0.03 and 0.22 +/- 0.04; for butylbenzene 0.47 +/- 0.06 and 0.31 +/- 0.04; for alpha-pinene 0.47 +/- 0.07 and 0.10 +/- 0.05; for gamma-terpinene 0.37 +/- 0.04 and 0.12 +/- 0.06; for p-cymene 0.74 +/- 0.05 and 0.36 +/- 0.07; for 2-methyl-2-hexanol 0.44 +/- 0.06 and 0.29 +/- 0.06. The uptake measurements also yielded values for the product HD(l)(1/2) for most of the molecules studied (H = Henry's law constant, D(l) = liquid-phase diffusion coefficient). Using calculated values of D(l), the Henry's law constants (H) for these molecules were obtained as a function of temperature. The H values at 298 K in units 10(3) M atm(-1) are as follows: for m-xylene (0.48 +/- 0.05); for ethylbenzene (0.50 +/- 0.08); for butylbenzene (3.99 +/- 0.93); for alpha-pinene (0.53 +/- 0.07); for p-cymene (0.23 +/- 0.07); for 2-methyl-2-hexanol (1.85 +/- 0.29).     

Complexation of Nickel(II) with Guanosine 5'-Monophosphate and Inosine 5'-Monophosphate: A Potentiometric and Calorimetric Study

The constants (K(s)) and enthalpies (DeltaH(s)) for stacking interactions between purine nucleoside monophosphates were determined by calorimetry; the values thus obtained were guanosine as follows: K(s) = 2.1 +/- 0.3 M(-)(1) and DeltaH(s) = -41.8 +/- 0.8 kJ/mol for adenosine 5'-monophosphate (5'AMP); K(s) = 1.5 +/- 0.3 M(-1) and DeltaH(s) = -42.0 +/- 1.5 kJ/mol for guanosine 5'-monophosphate (5'GMP); and K(s) = 1.0 +/- 0.2 M(-1) and DeltaH(s) = -42.3 +/- 1.1 kJ/mol for inosine 5'-monophosphate (5'IMP). The interaction of nickel(II) with purine nucleoside monophosphates was studied using potentiometric and calorimetric methods, with 0.1 M tetramethylammonium bromide as the background electrolyte, at 25 degrees C. The presence in solution of the complexes [Ni(5'GMP)(2)](2)(-) and [Ni(5'IMP)(2)](2)(-) was observed. The thermodynamic parameters obtained were log K(ML) = 3.04 +/- 0.02, log K(ML2) = 2.33 +/- 0.02, DeltaH(ML) = -18.4 +/- 0.9 kJ/mol and DeltaH(ML2) = -9.0 +/- 1.9 kJ/mol for 5'GMP; and log K(ML) = 2.91 +/- 0.01, log K(ML2) = 1.92 +/- 0.01, DeltaH(ML) = -16.2 +/- 0.9 kJ/mol and DeltaH(ML2) = -0.1 +/- 2.3 kJ/mol for 5'IMP. The relationships between complex enthalpies and the degree of macrochelation, as well as the stacking interaction between purine bases in the complexes are discussed in relation to previously reported calorimetric data.     

Effects of methyl substituent on the charge-transfer complexations of dicarbazolylalkanes with p-chloranil, tetracyanoethylene and tetracyanoquinodimethane

Series of 1,n-dicarbazolylalkanes and 1,n-di(3-methylcarbazolyl)alkanes (where n=1-5) were synthesized and the molar extinction coefficients, equilibrium constants, enthalpies, and entropies of their charge-transfer (CT) complexes with the π-acceptors p-chloranil, tetracyanoethylene, and tetracyanoquinodimethane were investigated. 1,n-Di(3-methylcarbazolyl)alkanes formed CT complexes with higher equilibrium constants, more negative enthalpies and entropies than 1,n-dicarbazolylalkanes. Vibrational spectra of CT complexes of one of the donor molecules (1,4-dicarbazolylbutane) with all three acceptors were compared.     

Kinetic studies of the reactions of O2(b 1sigma(g)+) with several atmospheric molecules

Thermal rate coefficients for the removal (reaction + quenching) of O2(1sigma(g)+) by collision with several atmospheric molecules were determined to be as follows: O3, k3(210-370 K) = (3.63 +/- 0.86) x 10(-11) exp((-115 +/- 66)/T); H2O, k4(250-370 K) = (4.52 +/- 2.14) x 10(-12) exp((89 +/- 210)/T); N2, k5(210-370 K) = (2.03 +/- 0.30) x 10(-15) exp((37 +/- 40)/T); CO2, k6(298 K) = (3.39 +/- 0.36) x 10(-13); CH4, k7(298 K) = (1.08 +/- 0.11) x 10(-13); CO, k8(298 K) = (3.74 +/- 0.87) x 10(-15); all units in cm3 molecule(-1) s(-1). O2(1sigma(g)+) was produced by directly exciting ground-state O2(3sigma(g)-) with a 762 nm pulsed dye laser. The reaction of O2(1sigma(g)+) with O3 was used to produce O(3P), and temporal profiles of O(3P) were measured using VUV atomic resonance fluorescence in the presence of the reactant to determine the rate coefficients for removal of O2(1sigma(g)+). Our results are compared with previous values, where available, and the overall trend in the O2(1sigma(g)+) removal rate coefficients and the atmospheric implications of these rate coefficients are discussed. Additionally, an upper limit for the branching ratio of O2(1sigma(g)+) + CO to give O(3P) + CO2 was determined to be < or = 0.2% and this reaction channel is shown to be of negligible importance in the atmosphere.     

Synthesis and cytotoxicity of dinuclear complexes containing ruthenium(II) bipyridyl units linked by a bis(pyridylimine) ligand

Enantiopure dinuclear ruthenium polypyridyl complexes of the form [Ru(2)(LL)(4)L(1)](PF(6))(4) (LL = 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen); L(1)= C(25)H(20)N(4) a bis(pyridylimine) ligand containing a diphenylmethane spacer) have been synthesized using the chiral building blocks cis-[Ru(bpy)(2)(py)(2)](2+) and cis-[Ru(phen)(2)(py)(2)](2+). These dinuclear ruthenium complexes have been characterised using NMR, mass spectrometry, UV-visible absorbance, circular dichroism and linear dichroism. The compounds exhibit good photo and thermal stability. The extinction coefficient for the bpy complex at 478 nm is epsilon(478) = 15,700 mol(-1) cm(-1) dm(3) and for the phen complex is epsilon(478) = 24,900 mol(-1) cm(-1) dm(3). Both complexes have their longest wavelength (metal to ligand charge transfer) transition predominantly x/y (short axis)-polarised while the transitions at shorter wavelength are a mixture of x/y and z-polarisations, similar to both the copper helicate and iron triple helicate studied previously. Cytotoxicity studies reveal that the compounds are dramatically less active against cancer cell lines than the recently reported supramolecular cylinders prepared from the same bis(pyridylimine) ligand.     

Spectrophotometric investigation of the reaction of eriochrome cyanin RC and magnesium and aluminium

The reaction of magnesium or aluminium ions with Eriochrome Cyanin RC in alkaline medium leads to formation of a complex of type ML. The molar absorptivities of the complexes are 1.90 +/- 0.14 x 10(3)1. mole(-1).cm(-1) at 570 nm for the magnesium complex and 3.87 +/- 0.04 x 10(4) at 555 nm for the aluminium complex. The conditional stability constants of the complexes were determined at various pH values, and hence the overall formation constants, which were found to be log beta(111) = 8.65 +/- 0.06 for MgOHL, log beta(121) = 22.29 +/- 0.05 for AlH(2)L, log beta(111) = 18.25 +/- 0.14 for AlHL, and log beta(101) = 13.66 +/- 0.01 for AlL.     

Spectroscopic and optimization modeling study of nitrous acid in aqueous solution

Nitrous acid (HONO) and the nitrite ion represent a particularly important conjugate pair of trace species with regard to heterogeneous behavior within the bulk, and on the surface, of aqueous atmospheric dispersions: this role results from their chemical reactivity, photolysis pathways, solubility, and ambient concentration levels. The actual ratio of NO(2)(-): HONO in solution is determined by the pH and the nitrous acid dissociation constant (pK(a)) which is generally quoted in the literature as 3.27 at 298 K. However there is much disagreement in published works as to the exact value, which should be used in model calculations relevant to the atmosphere. Furthermore even though the nitrite ion is known to absorb solar radiation in the 300-400 nm region and represents a dominant source of *OH radicals in surface seawater, large variations in the measured molar decadic absorption coefficients, epsilon, for nitrite ions (and aqueous HONO) are evident in the literature. In the current study, using a UV-vis spectrometric approach with careful baseline subtraction, the relevant epsilon values for the nitrite ion were determined to be 8.16 +/- 0.08 M(-1) cm(-1) for the npi transitions at 290 nm and 22.1 +/- 0.22 M(-1) cm(-1) at 354 nm. For HONO, the wavelength maximum for the strongest vibronic band in solution was found at 372 nm with an epsilon value of 60.52 +/- 0.6 M(-1) cm(-1). Using the Henderson-Hasselbalch equation and the above data, a value of 2.8 +/- 0.1 is therefore reported here for the pK(a) of nitrous acid. A Newton-Gauss method was then employed to solve a set of nonlinear equations defining the chemical speciation model for HONO in solution using an algorithm written in FORTRAN 90. A model based on a simple one-step protonation worked well for intermediate pHs (6-3) but departed from the experimental observations in highly acidic media. A two-step equilibrium model involving the nitroacidium ion, H(2)ONO(+), gave a much closer fit in the very acidic region, while having little or no effect on the pH 6-3 section of the profile.     

Mechanism of CO exchange on cis-[M(CO)2X2]- complexes (M=Rh,Ir;X=Cl, Br, or I)

The CO exchange on cis-[M(CO)2X2]- with M = Ir (X = Cl, la; X = Br, 1b; X = I, 1c) and M = Rh (X = Cl, 2a; X = Br, 2b; X = I, 2c) was studied in dichloromethane. The exchange reaction [cis-[M(CO)2X2]- + 2*CO is in equilibrium cis-[M(*CO)2X2]- + 2CO (exchange rate constant: kobs)] was followed as a function of temperature and carbon monoxide concentration (up to 6 MPa) using homemade high gas pressure NMR sapphire tubes. The reaction is first order for both CO and cis-[M(CO)2X2]- concentrations. The second-order rate constant, k2(298) (=kobs)[CO]), the enthalpy, deltaH*, and the entropy of activation, deltaS*, obtained for the six complexes are respectively as follows: la, (1.08 +/- 0.01) x 10(3) L mol(-1) s(-1), 15.37 +/- 0.3 kJ mol(-1), -135.3 +/- 1 J mol(-1) K(-1); 1b, (12.7 +/- 0.2) x 10(3) L mol(-1) s(-1), 13.26 +/- 0.5 kJ mol(-1), -121.9 +/- 2 J mol(-1) K(-1); 1c, (98.9 +/- 1.4) x 10(3) L mol(-1) s(-1), 12.50 +/- 0.6 kJ mol(-1), -107.4 +/- 2 J mol(-1) K(-1); 2a, (1.62 +/- 0.02) x 10(3) L mol(-1) s(-1), 17.47 +/- 0.4 kJ mol(-1), -124.9 +/- 1 J mol(-1) K(-1); 2b, (24.8 +/- 0.2) x 10(3) L mol(-1) s(-1), 11.35 +/- 0.4 kJ mol(-1), -122.7 +/- 1 J mol(-1) K(-1); 2c, (850 +/- 120) x 10(3) L mol(-1), s(-1), 9.87 +/- 0.8 kJ mol(-1), -98.3 +/- 4 J mol(-1) K(-1). For complexes la and 2a, the volumes of activation were measured and are -20.9 +/- 1.2 cm3 mol(-1) (332.0 K) and -17.2 +/- 1.0 cm3 mol(-1) (330.8 K), respectively. The second-order kinetics and the large negative values of the entropies and volumes of activation point to a limiting associative, A, exchange mechanism. The reactivity of CO exchange follows the increasing trans effect of the halogens (Cl < Br < I), and this is observed on both metal centers. For the same halogen, the rhodium complex is more reactive than the iridium complex. This reactivity difference between rhodium and iridium is less marked for chloride (1.5: 1) than for iodide (8.6:1) at 298 K.     

Disulphides of dithiophosphinic acids as analytical reagents-I Extractive spectrophotometric determination of palladium with some bis(dialkylthiophosphoryl)- and bis(diarylthiophosphoryl)disulphides

The disulphides of dithiophosphinic acids (DS) with the general formula R(2)P(S)SSP(S)R(2), where R = C(2)H(5), C(3)H(7), C(5)H(11), C(6)H(5) (I-IV) form coloured complexes of 1:3 stoichiometry with Pd(II). The absorption maxima and molar absorptivities are: a lambda(I) = 302 nm, epsilon(I) = 2.04 x 10(4) 1.mole(-1).cm(-1); lambda(II) = 305 nm, epsilon(II) = 2.58 x 10(4); lambda(III) = 303 nm, epsilon(III) = 2.60 x 10(4); lambda(IV) = 315 nm, epsilon(IV) = 3.25 x 10(4). The reaction takes about 3 min at room temperature, and the colour is stable for 24 hr. The influence of time, pH, reagent concentration, organic solvents and interferences have been studied. An extractive photometric method of determination of Pd(II) is described and applied to the determination of Pd(II) in a mixture of platinum metals.