Ruthenium(III) catalyzed oxidation of 1-phenylethanol and substituted 1-phenylethanols by phenyliodosoacetate

Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of LProline by Hexacyanoferrate(III) in Aqueous Alkali

Abstract: Kinetics of ruthenium(III) catalyzed oxidation of L-proline by hexacyanoferrate(III)(HCF) in alkali was studied spectrophotometrically at 30 0 C. A reaction was found to be independent upon (L-proline). The reaction was occurred without intervening free radical. Since unit order each in (Ru(III)) and (HCF), the oxidation follows an outer-sphere mechanism. A suitable mechanism was proposed and rate law was derived as kobs = kK

Os (VIII) Catalyzed Oxidative Cleavage of Pyrrolidine Ring in L-Proline by Sodium Periodate (NaIO4) in Alkaline Medium

Abstract: The present paper deals with the kinetic and mechanistic investigation of Os(VIII) catalyzed oxidation of proline by sodium periodate (NaIO4) in alkaline medium in temperature range 30 0 C to 45 0 C. The experimental result shows a first order kinetics with respect to Os[VIII] and [Periodate] while positive effect with respect to substrate i.e., Proline was observed. The reaction showed negative effect for [OH ]. Negligible effect of [HgOAc)2] and ionic strength of the medium was observed. The reaction is carried out in presence of mercuric acetate as a scavenger. The reaction between sodium periodate and proline in alkaline medium shows 2:1 stoichiometry. The values of rate constants observed at different temperatures (30 to 45 0 C) were utilized to calculate the activation parameters. A mechanism involving the complex formation between catalyst, substrate and oxidant has been proposed. L-glutamic acid has been identified as main oxidation product of the reaction chromatographically and spectroscopically. Based on kinetic data, reaction stiochiometry and product analysis of the reaction a feasible mechanism has been proposed. The rate law has been derived from obtained kinetic data.

Advanced Inorganic Chemistry

Abstract: For more than a quarter century, Cotton and Wilkinson's Advanced Inorganic Chemistry has been the source that students and professional chemists have turned to for the background needed to understand current research literature in inorganic chemistry and aspects of organometallic chemistry. Like its predecessors, this updated Sixth Edition is organized around the periodic table of elements and provides a systematic treatment of the chemistry of all chemical elements and their compounds. It incorporates important recent developments with an emphasis on advances in the interpretation of structure, bonding, and reactivity.From the reviews of the Fifth Edition:* "The first place to go when seeking general information about the chemistry of a particular element, especially when up-to-date, authoritative information is desired." -Journal of the American Chemical Society.* "Every student with a serious interest in inorganic chemistry should have [this book]." -Journal of Chemical Education.* "A mine of information . . . an invaluable guide." -Nature.* "The standard by which all other inorganic chemistry books are judged."-Nouveau Journal de Chimie.* "A masterly overview of the chemistry of the elements."-The Times of London Higher Education Supplement.* "A bonanza of information on important results and developments which could otherwise easily be overlooked in the general deluge of publications." -Angewandte Chemie.

The preparation and reactions of hydridochlorotris(triphenylphosphine)ruthenium(II) including homogeneous catalytic hydrogenation of alk-1-enes

Abstract: The complex hydridochlorotris(triphenylphosphine)ruthenium(II) as a benzene solvate, RuClH(PPh3)3,C6H6, has been obtained by the interaction of the dichloride, RuCl2(PPh3)3, with molecular hydrogen at ambient temperature pressure in the presence of a base such as triethylamine; other preparative methods are described. The corresponding bromide, RuBrH(PPh3)3,C6H6, has been prepared. From the chloride by interaction with norbornadiene and 2,2′-bipyridyl, the complexes RuClH(C7H8)(PPh3)2 and [RuClH(bipyr)(PPh3)2]2 respectively have been obtained; the complex RuH2(CO)(PPh3)3 has also been prepared.The complex RuClH(PPh3)3 is the most active catalyst yet discovered for the homogeneous hydrogenation of alk-1-enes in benzene or toluene solution. The interaction is highly specific and rates for other types of alkene are slower by a factor of at least 2 × 103. The inherent difficulties of the system however preclude detailed kinetic study and it is shown that slow poisoning of the catalyst occurs under hydrogenation conditions.N.m.r. studies of the hydrido-complex and its deuteride have allowed hydrogen atom exchange studies to be made. Isomerisation of alkenes is studied. The slow exchange between molecular hydrogen and the α-proton of a phenyl group on the phosphine is demonstrated.