金属有机化学第七章新.pptVIP

C-C bond formation by C-H activation of aromatic molecules;Examples where the C-H activation is promoted by coordination to a Lewis-basic functional group are very common.;Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;There are a large number of examples of this type of transformation in which an electrophilic metal center is used to activate a C-H bond on an aromatic center. Typically this occurs by an electrophilic aromatic substitution mechanism.;Periana (Chem. Commun. 2002, 2000 and JACS, 2004, 126, 352) has developed a method to couple benzene and alkenes to give alkyl benzenes. Although a similar reaction can be carried out under acidic conditions (Friedel-Crafts), only isopropylbenzene is produced. Using a metal catalyst, the major product is the more industrially useful linear isomer.;Alkane Functionalization Alkane functionalization reviews: Acc. Chem. Res. 1995, 164. Chem. Rev. 2001, 101, 953-996 J. Chem. Soc., Dalton Trans. 2001, 2437-2450 J. Mol. Cat. A.: Chem. 2004, 230, 7-25;The Bergman systems are very efficient at oxidatively adding C-H bonds. However efforts to transform the resulting metal-alkyl to a functionalized organic product have met with limited success.;Selective Oxidation of Alkanes: Shilov-type oxidation of methane;Reactivity of H-CH3 100 X higher than that of H-CH2OH;Catalytic System (Roy Periana, now at USC): Science, 1998, 280, 560;Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;In principle an industrially viable series of processes can be envisioned:;Problems limiting commercial application: 1) Turnover frequencies are 2 orders of magnitude too low 2) MeOH recovery from concentrated sulfuric acid is too costly 3) SO2 reoxidation to sulfuric acid is impractical;Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;The first catalytic s