Metallic nanoparticles isomerization

In addition to dissociation and isomerization, the process of forming new chemical bonds and larger structures can also be enhanced or controlled with surface plasmon excitations. Here I would like to highlight the plasmon-assisted formation of rather larger structures than the simple molecular systems discussed so far metal nanoparticles themselves and polymeric materials. 

R418 M. Krahk, B. Corain and M. Zecca, Catalysis by Metal Nanoparticles Supported on Functionalized Polymers , Chem. Pap., 2000, 54, 254 R419 Zh.A. Krasnaya, Dienone 2H-Pyran Valence Isomerization , Chem.-Heterocycl.Compd. (N. Y.), 1999, 35, 1255 R420 H.-M. Krenzlin, Dynamics of Complex Molecules and Multidimensional Nuclear Magnetic Resonance , Ber. Forschungszent. Juelich, 1999,(Juel-3726), i-iii, 1-125... 

Lewis acidic nanoscaled metal fluorides were successfully used as cataljdically active support for platinum and palladium. These catalysts were found to be very efficient in n-pentane hydroisomerization reactions [71]. In situ preparation is an efficient approach toward very small precious metal nanoparticles (2 nm) finely distributed over the fluoride catalyst that exhibit very good activity, stability, and selectivity toward isomerization (up to nearly 1(X)%) at 350°C. The exciting requisite for this superior catalytic behavior has been shown to be the combination of very strong Lewis acidity of the HS-AIF3 with C-H and/or C-F bond activation... 

The adsorption of chemical compounds on nanoparticles of synthesized composites not only leads to electrical sensor effects, but also can result in new catalytic processes caused by the surface properties of such nanoparticles [61]. The important catalytic properties of PPX-metal composites prepared via cry-ochemical vapor deposition synthesis were discovered while studying the isomerization of 3,4-dichlorobutene into trans- and cw-l,4-dichlorobutene catalyzed by Pd nanoparticles of Pd-PPX [64] and the reaction C-Cl bonds metathesis in the mixture of n-decane with CCI4 catalyzed by Cu nanoparticles of Cu-PPX [76]. 

Two major pathways in the thermolysis of metal carbonyls in polar media are realized. First, the disproportionation products react with the polymeric chain and initiate the side reactions of crosslinking, destruction, and isomerisation of the chain as well as the immobilization of mononuclear carbonyl complexes. For example, the polybutadiene containing 92% cis-, A- 4% trans-1,4- and4% 1,2-units (M= 246 000) undergoes isomerization when reacted with Fe3(CO)i2 for 2 h at 350K. This increases the trans-1,4 content to 76%. Simultaneously, significant particle enlargement occurs as the hot metal atoms form 1-10-nm nanoparticles (scheme 14). 

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