A new reaction mechanism for the iron-catalyzed cross-coupling reaction of ArMgX with alkyl halides using (TMEDA)FeAr(2) and (TMEDA)Fe(Ar)Br is proposed on the basis of the isolation and reaction of these organoiron intermediates.
The combination of IrCl(CO)(PPh3)2 with 1,1,3,3-tetramethyldisiloxane or poly(methylhydrosiloxane) (PMHS) is found to be an efficient catalyst system for the preparation of aldenamines from carboxamides; in particular, facile removal of silicone and iridium residues from the product can be achieved by the use of PMHS.
The organometallic polymer, CsoPd,, is prepared from c 6 0 and a PdO precursor, and the palladium to c60 ratio ( n ) can be varied by thermal disproportionation.Recent explosive developments of research on C6() and other spherical carbon clusters have provided fruitful contributions to understanding physical properties and chemical reactivities of these super aromatic molecules.1.2 An interesting feature of Cb0 is the high reactivity of its surface towards metallic species;Fagan and coworkers reported (q2-C60)Pt(PPh3)2 and [(Cs-Me5Ru+),l(C60)]rl+ as the first organometallic complexes including the coordination of n-electrons in C6() to the transition metal centre.3 Several metallic species bound to the surface of Cm were also detected in the gas phase.4 In this
The synergetic effect of two Si-H groups leads to efficient reduction of carboxamides to amines by platinum catalysts under mild conditions. The rate of the reaction is dependent on the distance of two Si-H groups; 1,1,3,3-tetramethyldisiloxane (TMDS) and 1,2-bis(dimethylsilyl)benzene are found to be an effective reducing reagent. The reduction of amides having other reducible functional groups such as NO(2), CO(2)R, CN, C horizontal lineC, Cl, and Br moieties proceeds with these groups remaining intact, providing a reliable method for the access to functionalized amine derivatives. The platinum-catalyzed reduction of amides with polymethylhydrosiloxane (PMHS) also proceeds under mild conditions. The reaction is accompanied by automatic removal of both platinum and silicon wastes as insoluble silicone resin, and the product is obtained by simple extraction. A mechanism involving double oxidative addition of TMDS to a platinum center is discussed.
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