Organosilanes selectivity

A pletliora of different SA systems have been reported in tire literature. Examples include organosilanes on hydroxylated surfaces, alkanetliiols on gold, silver, copper and platinum, dialkyl disulphides on gold, alcohols and amines on platinum and carboxyl acids on aluminium oxide and silver. Some examples and references can be found in [123]. More recently also phosphonic and phosphoric esters on aluminium oxides have been reported [124, 125]. Only a small selection out of tliis number of SA systems can be presented here and properties such as kinetics, tliennal, chemical and mechanical stability are briefly presented for alkanetliiols on gold as an example. 

A catalyst, usually acid, is required to promote chemoselective and regioselective reduction under mild conditions. A variety of organosilanes can be used, but triethylsilane ia the presence of trifiuoroacetic acid is the most frequendy reported. Use of this reagent enables reduction of alkenes to alkanes. Branched alkenes are reduced more readily than unbranched ones. Selective hydrogenation of branched dienes is also possible. 

Fluormated organosilanes are used as reagents for the construction of carbon-carbon bonds and for the selective synthesis of phosphate esters... 

One of the remarkable features of these 14 electron fragments, which were developed experimentally on the basis of applied MO theory considerations, is their ability to attack selected C-H and, in particular, unactivated C-Si bonds of various organosilanes. Mechanism studies of these bond activation reactions at this point suggest a new type of a-complexation in a common transition state or intermediate for both C-H and C-Si activation, which has to be further investigated in detail through experiments and by theory. 

The selective organosilane reduction of ketone functions can be effected in the presence of a number of other functional groups including epoxides,320,366 ketals,86,367 thioketals,368 other ketones,369,370 /1-lactams,371 alkynes,372 esters,79,80,83,84,87,320,373,374 a-bromides,76,80,83 amides80,83,84,86,276,320,375... 

Figure 5.9 TEMPO DE is obtained by electrodeposition of a thin layer of orga-nosilica doped with TEMPO (2,2,6,6-tetramethylpiperidine-l-oxyl) upon application of — 1.1 V (v.v. Ag/AgCl) for 15 min to a solution of suitable organosilanes (left). The electrocatalytic film thereby obtained selectively converts benzyl alcohol dissolved in 0.2 M NaHC03 (right). 

Various fabrication schemes have emerged using this approach. A common one is the site-selective photochemical etching of an organosilane-modified surface by irradiation through a mask [86]. This results in a chemically patterned surface with active sites, where modified ONDs can be attached, surrounded by bare (irradiated) regions. 

A modified concept for the generation of partially crosslinked expanded PP films and sheets for use in automotive applications is presented. An optimised formulation window for the organosilane crosslinking of selected PP copolymers is described in detail. 5 refs. 

A comparison of steric influence resulting from more than 80 different silyl groups is summarized in Table 1. The trend is established on the basis of reaction yields, rates and selectivity, as well as on reactivity and physical properties of organosilanes. Two different effects may be involved (a) the effect of a silyl group on reactions taking place at the neighboring centers, and (b) the effect of the groups attached to silicon on the nucleophilic attack at the silicon atom. 

It is the purpose of this chapter to review selectively the advances in the synthetic applications of organosilicon compounds, excluding those organosilanes covered in other chapters. Since the publication of The Chemistry of Organic Silicon Compounds, two monographs1,2 and several reviews3-5 have been published, as have three conference proceedings6-8 and a symposium-in-print 9. 

Chemical methods are generally based on the reaction of surface hydroxyl groups with a selectively reacting compound to form a covalently bonded surface species of well known composition. As reactive compounds, diborane,4,5 boron trichloride,6,7 diazomethane,8 organosilanes,3,6,9,10,11,12,13,14 and organometallic compounds15 have been employed. a0H is then derived from the amount of the chemisorbed species as well as the amount of volatile reaction products. 

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