By Shinji Murai
The important thought of this quantity is to supply a Capita Selecta of unconventional and thought-provoking issues in organometallic chemistry, awarded by way of specialists in every one box. As meant, this strategy leads both to studies masking a particular unusual classification of organometallic compounds or to overviews which relate unusual actual houses with a number of sessions of organometallic compounds. content material: constitution and electrochemistry of transition steel carbonyl clusters with interstitial or semi-interstitial atoms: distinction among nitrides or phosphides and carbides / Piero Zanello -- strange nuclear magnetic defensive and coupling constants with regards to strange bonding occasions / Bernd Wrackmeyer -- Deuterium spin lattice rest and deuterium quadrupole coupling constants. a singular technique for characterization of transition steel hydrides and dihydrogen complexes in resolution / Vladimir I. Bakhmutov -- NMR stories of ligand nuclei in organometallic compounds -- new info from solid-state NMR ideas / man M. Bernard, Roderick E. Wasylishen -- steel atom movement in a few iron organometallics / Rolfe H. Herber -- Magnetic conversation in binuclear organometallic complexes mediated by means of carbon-rich bridges / Frďřic Paul, Claude Lapinte -- Molecular cluster complexes with facial arene ligands / Herbert Wadepohl -- Cobaltafulvenes and cobaltapentalenes: hugely polar metallacyclic II-systems with strange houses / Herbert Wadepohl -- Novel hugely nucleophilic ylidic ligands for the instruction of strangely sturdy steel complexes / Norbert Kuhn, Martin Göhner, Gernot Frenking, Yu Chen -- Supramolecular interactions in constructions of natural antimony and Bismuth compounds / Gabor Balz̀s, Hans Joachim Breunig. summary: The central suggestion of this quantity is to provide a Capita Selecta of unconventional and thought-provoking issues in organometallic chemistry, provided via specialists in each one box. As meant, this method leads both to studies protecting a particular unusual classification of organometallic compounds or to overviews which relate unusual actual houses with quite a few periods of organometallic compounds
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Additional info for Activation of Unreactive Bonds and Organic Synthesis
76 Topics in Organometallic Chemistry, Vol. 3 Volume Editor: S. Murai © Springer-Verlag Berlin Heidelberg 1999 48 Fumitoshi Kakiuchi, Shinji Murai 1 Introduction One of the most valuable synthetic methods in organic synthesis is the direct use of otherwise unreactive C–H bonds with the aid of transition metal complexes. Since Kleiman and Dubeck reported in 1963 the possibility of cleavage of C–H bonds in azobenzene by Cp2Ni complex , many research groups have reported the cleavage of C–H bonds by using stoichiometric amounts of transition metal complexes .
35) . They found that rhenium polyhydride complex catalyzes dehydrogenation of cycloalkane to cycloalkene in the presence of tert-butylethylene as the hydrogen acceptor. The 62 Fumitoshi Kakiuchi, Shinji Murai turnover number in this system was only 9. However, their result indicates the possibility of alkane dehydrogenation by a soluble transition metal catalyst. + But ((p-F-C6H4)3P)2ReH7 + 80 °C, 10 min But (35) 9 TON Several thermal catalytic dehydrogenations of alkanes in the presence of alkenes as the hydrogen acceptor have been reported by several research groups [67–76].
Activation of C–H Bonds: Stoichiometric Reactions 29 Scheme 7. [BArF]. This cation is more reactive than Cp*Ir(PMe3)(CH3)OTf and reacts with terminal C–H bonds of alkanes such as pentane and methylcyclohexane to eliminate methane and give oleﬁn hydride complexes, similar to the reaction with ethane shown in Scheme 7 . One mechanism for these exchanges has been recently proposed by Chen based upon a combination of gas phase, solution phase, and computational studies. The mechanism involves cyclometallation of the PMe3 ligand to give an IrV intermediate, followed by methane loss, followed by oxidative addition of an alkane C–H bond with opening of the metallacycle .
Activation of Unreactive Bonds and Organic Synthesis by Shinji Murai