| AUTHOR |
TITLE |
Chandra, S. K.,
Gould, E. S. |
Electron Transfer. 130. Reductions with Indium(I)1
Inorganic Chemistry; 1996; 35(13); 3881-3884. (Article) |
Experimental Section
Kinetic Experiments. Reactions, under argon, were examined at the high wavelength maximum of the CoIII complex, using either a Beckman Model 5260 recording spectrophotometer, a Cary 14 instrument, or a Durrum-Gibson stopped-flow spectrophotometer interfaced with an OLIS computer system. Ionic strength, which was regulated by addition of LiClO4 and HClO4, was maintained at 0.2 M. Excess quantities of oxidant were generally used and concentrations were most often adjusted so that no more than 10% of the latter was consumed in reaction. All rapid reactions yielded simple exponential curves, and rate constants in such cases were obtained by nonlinear least-squares fitting to the relationship describing first-order decay. Values obtained from replicate runs agreed to better than 5%. These reactions were first order in both redox partners. Profiles exhibited no indication of transients formed or destroyed on a time scale comparable to that of the Co(III)-In(I) reaction. |
Chandra, S. K.,
Gould, E. S. |
Electron Transfer. 128. Rate Enhancements by Donor Sulfur in Hexadentate Ligands1
Inorganic Chemistry; 1996; 35(7); 2136-2139. (Article) |
Experimental Section
Kinetic Studies. Reactions of Cr(II), V(II), Eu(II), Ti(III), and N-methyldihydrophenazinium cation were carried out under N2, and those of Ru(NH3)62+ were run under argon. Conversions were monitored using a Beckman Model 5260 or Cary 14 recording spectrophotometer or a Durrum-Gibson stopped-flow spectrophotometer interfaced with an OLIS computer system. Reductions of the Co(III)-N2S2O2 complex were followed at 665 nm, whereas those of the Co(III)-N4O2 oxidant were observed at 584 nm. Ionic strength, which was maintained at 0.10 M for most reactions, was regulated by addition of LiClO4 and HClO4 or, in the case of reductions by Ru(NH3)62+, by addition of HCl. Because the N2S2O2 complex dissolves with difficulty in water, solutions of this oxidant were prepared by dissolving the solid compound in a small volume of CH3CN, then diluting 50-fold with the aqueous supporting medium. |
Shi, T.,
Elding, L. I. |
Kinetics and Mechanism for Formation of Olefin Complexes in the Reaction between Palladium(II) and Maleic Acid,
Inorganic Chemistry; 1998; 37(21); 5544-5549. |
Experimental Section
Apparatus.
Rate constants were evaluated by use of the Applied Photophysics software or the OLIS nonlinear least-squares minimizing kinetics program Model 4000 Data System Stopped-flow Version 9.04. |
Romeo, R.,
Plutino, M. R.,
Elding, L. I. |
Protonolysis of Dialkyl- and Alkylarylplatinum(II) Complexes and Geometrical Isomerization of the Derived Monoorgano-Solvento Complexes: Clear-Cut Examples of Associative and Dissociative Pathways in Platinum(II) Chemistry
Inorganic Chemistry; 1997; 36(25); 5909-5916. (Article) |
Experimental Section
Instrumentation
The kinetics at high pressure were followed by use of an HPSF-56 Hi-Tech high-pressure stopped-flow spectrophotometer equipped with a digital pressure indicator. Kinetic runs were evaluated by use of the OLIS Model 4000 Data System Stopped-Flow, version 9.04, software. |
Wendt, O. F.,
Oskarsson, A,
Leipoldt, J. G.,
Elding, L. I. |
Synthesis, Structure, and Reactivity of Arylchlorobis(dialkyl sulfide)platinum(II) Complexes
Inorganic Chemistry; 1997; 36(20); 4514-4519. (Article) |
Experimental Section
Kinetics. The kinetics were monitored on either a modified Durrum-Gibson stopped-flow instrument, a homebuilt stopped-flow spectrophotometer, or an Applied Photophysics Bio Sequential SX-17MV stopped-flow ASVD spectrofluorometer. The substitution of chloride on complexes 1, 2, 4, and 5 by various nucleophiles was studied in methanol solvent by observing the increase in absorbance at wavelengths between 280 and 330 nm. All reactions were studied under pseudo first-order conditions with at least a 10-fold excess of nucleophile (10-1-5 × 10-3 M) with respect to the complex (5 × 10-4 M). Data were analyzed by means of the OLIS program Model 4000 Data System Stopped-flow, version 9.04,27 or the software provided by Applied Photophysics. All kinetic traces fitted well to first-order exponentials. The observed rate constants were not affected by an increase of the ionic strength to 0.1 M or an addition of 1% water to the methanol. |
Shi, T.,
Elding, L. I. |
Linear Free Energy Relationships for Complex Formation Reactions between Carboxylic Acids and Palladium(II). Equilibrium and High-Pressure Kinetics Study
Inorganic Chemistry; 1997; 36(4); 528-536. (Article) |
Experimental Section
Apparatus. UV-visible spectra were recorded on a Milton Roy 3000 diode-array spectrophotometer. The kinetics was followed at ambient pressure by use of a modified Durrum-Gibson stopped-flow spectrophotometer or an Applied Photophysics Bio Sequential SX-17 MX stopped-flow ASVD spectrofluorimeter and, at elevated pressures, by use of a Hi-Tech high-pressure stopped-flow spectrophotometer, HPSF-56, equipped with a digital pressure indicator. Temperature was controlled to ±0.1 °C. Pseudo-first-order rate constants were evaluated using the OLIS nonlinear least-squares-minimizing kinetics program Model 4000 Data System Stopped-Flow Version 9.04 or the Applied Photophysics software package. |
Shi, T.,
Elding, L. I. |
Structure-Reactivity Correlations for Complex Formation Reactions between Square-Planar Metal Centers and Thioethers
Inorganic Chemistry; 1996; 35(20); 5941-5947. (Article) |
Experimental Section
Apparatus. UV-visible spectra were recorded on a Milton Roy 3000 diode-array spectrophotometer with thermostated 1.00 cm quartz Suprasil cells. The kinetics was followed at ambient pressure by use of a modified Durrum-Gibson stopped-flow spectrophotometer, or by an Applied Photophysics Bio Sequential SX-17 MX stopped-flow ASVD spectrofluorimeter, and at elevated pressures by use of a Hi-Tech high-pressure stopped-flow spectrophotometer, HPSF-56, equipped with a digital pressure indicator. Pseudo-first-order rate constants were evaluated by use of the OLIS nonlinear least-squares minimizing kinetic program Model 4000 Data System Stopped-Flow Version 9.04 or the Applied Photophysics software package. |
Elmroth, S. K. C.,
Elding, L. I. |
Competitive Substitution and Electron Transfer in Reactions between Haloamminegold(III) and Halocyanoaurate(III) Complexes and Thiocyanate
Inorganic Chemistry; 1996; 35(8); 2337-2342. (Article) |
Experimental Section
Calculations. All kinetic runs were evaluated by use of the OLIS "Model 4000 Data System Stopped-Flow", Version 9.04, software. Pseudo-first-order rate constants were calculated as an average of at least six independent kinetic runs. Second-order rate constants were obtained by a fit of the pseudo-first-order rate constants vs the concentration of free thiocyanate to a straight line by use of a least-squares routine. Enthalpies and entropies of activation for reduction of trans-Au(CN)2(SCN)2- were derived from a fit to the Eyring equation of the natural logarithm of the second-order rate constant vs 1/T. Volumes of activation were obtained by a fit of the variable-pressure data to eq 1, where k0 denotes the rate constant at 0.1 MPa and 24.7 °C. |
Shi, T.,
Elding, L. I. |
Equilibrium and High-Pressure Kinetic Study of Formation and Proton-Assisted Aquation of Monodentate Acetate, Propionate, and Glycolate Complexes of Palladium(II) in Aqueous Solution
Inorganic Chemistry; 1996; 35(3); 735-740. (Article) |
Experimental Section<
Apparatus. UV-visible spectra were recorded on a Milton Roy 3000 diode-array spectrophotometer with thermostated 1.00 cm quartz Suprasil cells. The kinetics were followed at ambient pressure by use of a modified Durrum-Gibson stopped-flow spectrophotometer and at elevated pressures by use of a Hi-Tech high-pressure stopped-flow spectrophotometer, HPSF-56, equipped with a digital pressure indicator. Kinetic data were evaluated using the OLIS nonlinear least-squares-minimizing kinetic program Model 4000 Data System Stopped-Flow Version 9.04. |
Macintosh, A. M.,
Nocera, D. G. |
Photoinduced Ligand Redistribution Chemistry of Quadruply Bonded Mo2Cl2(6-mhp)2(PR3)2 Complexes
Inorganic Chemistry; 1996; 35(24); 7134-7139. (Article) |
Experimental Section
Instrumentation and Procedures. Electronic absorption spectra were recorded on an OLIS-modified Cary 17D or Cary 2300 UV-vis-near-IR spectrometer. Extinction coefficients were calculated from Beer-Lambert plots composed of at least seven points. The emission spectra were obtained by exciting samples at 546.5 nm with the 200 W Hg/Xe lamp of a spectrometer designed and constructed at Michigan State University. Temperature-dependent emission spectra were obtained by controlling the temperature of microcrystalline solids with an Air Products cryogenic system. |
