By E. O. Fischer (auth.), U. Schubert (eds.)

There are just few themes in organometallic chemistry, that have inspired learn actions in as many components, as transition-metal carbene (alkylidene) complexes. approximately 25 years after the 1st deliberate synthesis of a carbene complicated in E.O. Fischer's laboratory in Munich the NATO complex learn Workshop on Transition-Metal Carbene Complexes used to be the 1st assembly which,brought jointly scientists from assorted disciplines to debate inorganic, natural, theoretical structural catalysis-related features of steel carbene chemistry. The seventieth birthday of Professor E.O. Fischer was once a very good get together for this firm. The organizers of the assembly (K.D. Dotz, Marburg; F.R. KreiBl, Munchen; U. Schubert, Wurzburg) have been inspired by means of the truth that many of the major scientists during this sector have been capable of perform the workshop. The very excessive common of the contributions is mirrored during this ebook, which incorporates papers from nearly all of the members. The lawsuits exhibit the cutting-edge in steel carbene chemistry and may with a bit of luck be a landmark within the improvement of this zone of chemistry. beneficiant monetary aid for the workshop and for the education of this e-book was once supplied through the clinical Affairs department of NATO and a few businesses. The organizers additionally recognize the efforts of the employees of the Bildungs­ zentrum der Hans-Seidel-Stiftung in Wild undesirable Kreuth for making a friendly and stimulating surroundings through the conference.

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H. Kletzin, H. Werner, O. L. Ziegler, Angew. Chem. Int. Ed. Engl. 22 (1983) 46. K. Roder and H. Werner, Angew. Chem. Int. Ed. Engl. 26 (1987) 686. L. H. Tulip, J. Amer. Chem. Soc. 103 (1981) 5984. L. H. Tulip, Organometallics 1 (1982) 1580. A. Herrmann, Angew. Chem. Int. Ed. Engl. 21 (1982) 117. A. A. Goddard III, Organometallics 7 (1988) 675. D. Mango and I. Dvoretzky, J. Amer. Chem. Soc. 88 (1966) 1654. A. Herrmann, Adv. Organometal. Chem. 20 (1982) 159. F. R. M. H. Wright, J. Amer. Chem. Soc.

14] In each of these reactions the involvement of an intermediate cationic methylene complex is postulated on the basis of observed products and none of the intermediates has been isolated or even detected in solution. [15] In this connection it is often assumed that migration of an alkyl ligand to a terminal methylene is irreversible and favoured over the related migration to a carbon monoxide ligand. One recent experiment, where there is opportunity for methyl to migrate either to CHZ or CO supports this preferential migration to CHZ·[IZ] *proposed intermediate However, recent ab initio calculations on model ruthenium systems [16] suggest that CH3 to CHZ migration is much less exothermic than H migration and subject to an activation barrier of 20-25 kcal mol- 1 Such migration reactions may not be facile even for later transition elements and compounds reported in this paper, where there is opportunity for aryl migration either to CH2 or to CO, invariably result in migration to CO.

22] The Q-tolyl compound is similar with trans-phosphines but the greater steric demands of the o-tolyl ligand result in a more trigonal disposition of the equatorial ligands. [23] Carbonylation of the ruthenium complex results in a rapidly established equilibrium mixture of an aryl/dicarbonyl compound and an n2-acyl/monocarbonyl compound. The position of this equilibrium is markedly dependent upon X and R. ;-- PPh3 X = Cl < Br < I E-tolyl - Ph < Q-tolyl The promotion of the acyl form by a bulky R-group has subsequently been observed in other systems.

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