By Peter Hofmann (auth.), Prof. Dr. Armin de Meijere, Prof. Dr. Heindirk tom Dieck (eds.)
More and extra attainable purposes of organometallic compounds in natural synthesis were exposed and increasingly more scientists are interested in this zone of analysis. This e-book offers an cutting-edge account of the profitable program of major- and transition steel mediated syntheses. it's going to stimulate new principles and start up extra learn in all parts of this attention-grabbing chemistry.
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Extra info for Organometallics in Organic Synthesis: Aspects of a Modern Interdisciplinary Field
Sample text
Ca. 380 - 460 kJ/mol for D(C-H», the C-H addition reaction typified by eqn. 3 is thus anticipated to generally be endothermic by several ten kJ/mol. The obvious strategy to overcome these thermodynamic limitations on C-H bond oxidative addition aims at stabilizing the alkyl hydride M(R)(H) with respect to the reactants RH and M by using coordinatively 39 unsaturated high-energy particles M which are likely to satisfy the requirements for forming comparatively strong bonds to hydrogen and, above all, to carbon.
The metal-dependent transition between intra- and intermolecular C-H addition observed for the two chelate phosphine complexes is clearly due to the different degrees of steric crowding and chelate ring strain in the required 16e d 8 -intermediates, because the M-Cl distances in the dichloro precursor complexes (PP 3 )FeCl 2 , 239 and 241 pm (Antberg 1985), and (PP 3 )RuCl 2 , 251 and 252 pm (Antberg 1986(b)), demonstrate that the covalent radius of the ruthenium atom stabilized 43 by the tripod tetrakis(tertiary) phosphine ligand is at least 10 pm larger than that of the iron atom in the same coordination environment.
Organometallics 6: 687-692 Organometallic Pinhas AR, Albright TA, Hofmann P, Hoffmann R (1980) A Class of Trinuclear Clusters with Carbonyl Bridging. Helv Chim Acta 63: 29-49 Rausch MD, Gastinger RG, Gardener SA, Brown R, Wood JS (1977) Isolation and Structural Characterization of a Pr'oduct Formally Derived from the Double Oxidative Addition of Benzene to Iridium. ,~-C~Me~ )-dicarbonyl-rhodium and -iridium Complexes. J Chem Soc, Chem Commun 1984: 624-626 Saillard JY, Hoffmann R (1984) C-H and H-H Activation in Transition Metal Complexes and on Surfaces.