Advances in Chemical Physics, Vol.70 Part 2, Evolution of by Ilya Prigogine, Stuart A. Rice

By Ilya Prigogine, Stuart A. Rice

Details at the evolution of dimension results in chemical dynamics is equipped by means of this e-book. assurance comprises structural versions for clusters produced in a loose jet enlargement, solid-liquid part behaviour in microclusters, the quantum mechanics of clusters, small cluster-reactions of van der Waals molecules, molecular floor chemistry, reactions of fuel ph ase steel clusters, vibrational leisure in condensed stages and activated expense techniques in condensed stages.

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CARBYNE TO CARBENB CONVERSION REACTIONS DIMET AL CENTRES AT HETERONUCLEAR F. GORDON A. STONE Department of Inorganic Chemistry The University Bristol SS8 1TS England ABSTRACT. Compounds with allcylidyne ligands bridging heteronuclear metal-metal alkyl or aryl) bonds provide an opportunity to study the chemistry of ,,-CR (R groups in a variety of different electronic and steric environments. Reactivity patterns are strongly influenced both by the nature of the group R, and by the metal-ligand fragments with which the ,,-CR ligands are associated.

A quite different reaction occurs when the d 6 ~ethylene complex Os(=CH2)(n2-C[0]~-tolyl)Cl(PPh3)2 is treated with CO. Two products are formed, one is colourless and cationic, the other bright yellow and neutral. Both compounds contain a metallaoxetene ring, Os=CROCH2, formed by the oxygen of the acyl ligand adding to the methylene carbon. /I ~C·/ ' PPh3 R , 10% yellow v(CO) 1921 cm- 1 With Ru(=CH2)(n2-C[0]R)Cl(PPh3)2 and CO only the cationic metallaoxetene is formed and with isocyanide a similar reaction ensues.

Reactivity patterns are strongly influenced both by the nature of the group R, and by the metal-ligand fragments with which the ,,-CR ligands are associated. Discussion will focus on reactions in which the alkylidyne fragment is converted into an alkylidene group. Often the alkylidyne to alkylidene step is followed by further transformations leading to products of many different structural types. V. Ashworth working in my laboratory discovered the reaction shown in Scheme 1. 1 The methodology of the synthesis of the tungsten-platinum compound (1) was based on the isolobal mapping between the fragments W(COh(71-CsHs) and CC6H4Me-4.

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