Platinum catalysts, hydrosilylation

All complexes have shown high catalytic activity, even at room temperature (in contrast to platinum catalysts). Hydrosilylation in the presence of phosphine-rhodium complexes occurred in air, because real catalyst (active intermediate) was formed after oxygenation and/or dissociation of phosphine, as reported previously [14]. The non-phosphine complexes 1 and 4 are also very efficient catalysts for the hydrosilylation of allyl glycidyl ether. Irrespective of the starting precursor, a tetracoordinated Rh-H species, responsible for catalysis, is generated under reaction conditions, as illustrated in Scheme 3. 

The a,oo-difunctional PDMS is obtained by cationic polymerization of octamethyl-cyclotetrasiloxane (D4) in the presence of a known amount of tetramethyldisiloxane, acting as a functional transfer agent. Hydrosilylation reaction is carried out in toluene solution at 90 °C with a platinum catalyst. 

Hydrosilylation with 2,4,6,8-tetramethylcyclotetrasiloxane has sometimes given uncontrollable exotherms or explosions in the laboratory. Use of safety screens and the lowest possible (<20 ppm) level of platinum catalyst are recommended. See VINYLSILOXANES... 

Well-defined complicated macromolecular structures require complex synthetic procedures/techniques and characterization methods. Recently, several approaches leading to hyperbranched structures have been developed and will be the focus of this section. The preparation of hyperbranched poly(siloxysilane) has been reported [198] and is based on methylvinyl-bis(dimethyl siloxysilane), an A2B type monomer, and a progressive hydrosi-lylation reaction with platinum catalysts. An appropriate hydrosilylation reaction on the peripheral - SiH groups led to the introduction of polymeric chain (PIB, PEO) or functional groups (epoxy, - NH2) [199]. 

The synthesis of precursors A and B (see Figure 12.10) has been described by Michalczyk et al. [102]. These compounds can be synthesised from platinum-catalysed hydrosilylation reactions, that is addition reactions between Si—H and C=C groups in the presence of a catalyst. Once the pure precursors are obtained, BSG can be synthesised by incorporation of calcium alkoxide during polycondensation of the precursors. 

The rhodium-catalyzed cyclization/hydrosilylation of internal diyne proceeds efficiently with high stereoselectivity (Scheme 106). However, terminal diynes show low reactivity to rhodium cationic complexes. Tolerance of functionalities seems to be equivalent between the rhodium and platinum catalysts. The bulkiness of the hydrosilane used is very important for the regioselectivity of the rhodium-catalyzed cyclization/hydrosilylation. For example, less-hindered dimethylethylsilane gives disilylated diene without cyclization (resulting in the double hydrosilylation of the two alkynes), and /-butyldimethylsilane leads to the formation of cyclotrimerization compound. 

Beyond palladium, it has recently been shown that isoelectronic metal complexes based on nickel and platinum are active catalysts for diyne reductive cyclization. While the stoichiometric reaction of nickel(O) complexes with non-conjugated diynes represents a robust area of research,8 only one example of nickel-catalyzed diyne reductive cyclization, which involves the hydrosilylative cyclization of 1,7-diynes to afford 1,2-dialkylidenecyclohexanes appears in the literature.7 The reductive cyclization of unsubstituted 1,7-diyne 53a illustrates the ability of this catalyst system to deliver cyclic Z-vinylsilanes in good yield with excellent control of alkene geometry. Cationic platinum catalysts, generated in situ from (phen)Pt(Me)2 and B(C6F5)3, are also excellent catalysts for highly Z-selective reductive cyclization of 1,6-diynes, as demonstrated by the cyclization of 1,6-diyne 54a.72 The related platinum bis(imine) complex [PhN=C(Me)C(Me)N=Ph]2Pt(Me)2 also catalyzes diyne hydrosilylation-cyclization (Scheme 35).72a... 

A separate, quite thorough study of terminal alkyne hydrosilylation with platinum arrived at a similar set of conditions.39 This work utilized a one-pot hydrosilylation with the preformed platinum(O) complex (>Bu3P)Pt[(CH2=CH)Me2Si]20 ([(CH2=CH)Me2Si]20 = DVDS) and subsequent palladium-catalyzed coupling reaction to demonstrate that the platinum catalyst is compatible with cross-coupling conditions, providing a convenient hydrocarbation of terminal alkynes (Table 2). 

Denmark pursued intramolecular alkyne hydrosilylation in the context of generating stereodefined vinylsilanes for cross-coupling chemistry (Scheme 21). Cyclic siloxanes from platinum-catalyzed hydrosilylation were used in a coupling reaction, affording good yields with a variety of aryl iodides.84 The three steps are mutually compatible and can be carried out as a one-pot hydro-arylation of propargylic alcohols. The isomeric trans-exo-dig addition was also achieved. Despite the fact that many catalysts for terminal alkyne hydrosilylation react poorly with internal alkynes, the group found that ruthenium(n) chloride arene complexes—which provide complete selectivity for trans-... 

The palladium-catalyzed asymmetric hydrosilylation of styrenes has been applied to the catalytic asymmetric synthesis of l-aryl-l,2-diols from arylacetylenes (Scheme 6).46 Thus, ( )-l-aryl-2-(trichlorosilyl)ethenes, which are readily generated by platinum-catalyzed hydrosilylation of arylacetylenes, were treated with trichlorosilane and the palladium catalyst coordinated with MOP ligand 12f to give 1 -aryl-1,2-bis(silyl)ethanes, oxidation of which produced the enantiomerically enriched (95-98% ee) 1,2-diols. 

While hydrosilylation of 1-alkenes and HSiCl3 with platinum catalysts provides linear products (1-trichlorosilylalkanes), palladium chloride modified with phosphines gives products carrying the trichlorosilyl group at the secondary carbon. This is highly remarkable because all other metal complexes studied so far lead to 1-substituted products. This regioselectivity leads to the possibility to carry out asymmetric hydrosilylation. 

The ratio of the three products depends on the reacting silane and alkyne, the catalyst, and the reaction conditions. Platinum catalysts afford the anti-Markovnikov adduct as the main product formed via syn addition.442- 146 Rhodium usually is a nonselective catalyst404 and generally forms products of anti addition.447 151 Minor amounts of the Markovnikov adduct may be detected. Complete reversal of stereoselectivity has been observed.452 [Rh(COD)Cl]2-catalyzed hydrosilylation with Et3SiH of 1-hexyne is highly selective for the formation of the Z-vinylsilane in EtOH or DMF (94-97%). In contrast, the E-vinylsilane is formed with similar selectivity in the presence of [Rh(COD)Cl]2-PPh3 in nitrile solvents. 

Detailed mechanistic studies with respect to the application of Speier s catalyst on the hydrosilylation of ethylene showed that the process proceeds according to the Chalk-Harrod mechanism and the rate-determining step is the isomerization of Pt(silyl)(alkyl) complex formed by the ethylene insertion into the Pt—H bond.613 In contrast to the platinum-catalyzed hydrosilylation, the complexes of the iron and cobalt triads (iron, ruthenium, osmium and cobalt, rhodium, iridium, respectively) catalyze dehydrogenative silylation competitively with hydrosilylation. Dehydrogenative silylation occurs via the formation of a complex with cr-alkyl and a-silylalkyl ligands ... 

Intramolecular hydrosilylations of functionalized alkenes followed by hydrogen peroxide oxidation provide powerful methods for organic syntheses86-88. The reactions of allylic O-dimethylsilyl ethers 59 promoted by platinum catalysts, e.g. Karstedt s catalyst and Pt(PPh3)2(CH2=CH2), or rhodium catalysts, e.g. Rh(acac)(COD) and [RhCl(CH2=CH2)2]2> proceed via 5-endo cyclization to give oxasilacyclopentanes 60 with a couple of exceptions in which siloxatanes 61 are formed (Scheme ll)87,89. 

In a similar manner, the hydrosilylation-polymerization of diallyl bisphenol A (278) with 275 in the presence of a platinum catalyst affords polymer 279 that possesses a relatively high glass transition temperature for siloxane polymers (Tg = 28-34 °C) and... 

Another method for preparing polysiloxane networks is to use the hydrosilylation reaction an SiH group is added to a double bond e.g., an allyl group with the help of a catalyst (platinum catalyst) ... 

The original use of hydrosilylation [117] in semi-IPN formation is attributed to Arkles [118-120]. His approach was to mix two polysiloxanes with the thermoplastic. One contained hydride functions and the other vinyl functions. The subsequent introduction of a platinum catalyst induced crosslinking. Depending on the number of hybrid and vinyl functions per chain, either chain-extension or crosslinking was observed. As pointed out by Arkles [119], according to theory, these phenomena should be obtained for a 1 1 hydride vinyl group ratio, however, in practice the hydride functions were consumed by several side reactions so that a higher hydride ratio was required. 

Very little has been reported so far on catalytic hydroboration and hydrosilylation in ionic liquids, which makes it difficult to judge whether they could offer significant improvements over existing methods. Platinum-catalysed hydrosilylation, for example, is a highly efficient process with catalyst loadings as low as 1 ppm relative to the substrate. Due to the low catalyst loading and the fact that hydrosilylation products are not for human consumption, efforts to remove the catalyst are from the final product are... 

The catalysts were tested in a model reaction of hydrosilylation of trimethylvi-nylsilane with 1,1,3,3-tetramethyldisiloxane (Scheme 4). A solution of both reagents in toluene ([Si-H] = 0.55 mol/dm [Si-H]/[-CH = CHJ = 1) was prepared. A solution in toluene of the immobilized platinum catalyst was added to the reaction mixture at room temperature ([Pt]/[-CH = CHJ = 1.7x 10 ). The amount of platinum in the catalyst, assuming that Pt coordinates to 3 -CH = CH2 moieties, was calculated on the basis of the relative decrease of vinyl groups in NMR spectrum [their number (related to Me groups) was compared to those in the precursor]. 

Scheme 4 Model hydrosilylation reaction catalyzed with platinum catalyst supported on T. -siloxane star-shape polymers...

We have described a new system of polymeric snpports based on multifunctional, exceptionally sterically hindered carbosilane moieties, grafted with block poly(vinylmethyl-co-dimethyl)siloxane arms. They offer uniformly periphery-distribnted active sites (-CH = CH moieties) and can be used for preparation of novel catalysts. Platinum was thus attached to the polymers via coordination to vinyl gronps. The materials used in hydrosilylation of vinylsilanes can be considered as an alternative for traditional platinum catalysts. The utility of the catalysts seems to be dependent on the ratio [D]/[V] in the copolysiloxane arm. Those with too high amonnt of vinyl groups suffer from poor solubility and catalytic performance dne to excessive inter/intra-chain coordinative cross-linking. 

In order to better characterize the system, a further kinetic study was carried out on these two catalysts. Hydrosilylation mechanism has been thoroughly studied in the literature. This is a complex system, since the mechanism depends altogether on the catalyst, the reactants and the experimental conditions. This also explains why for each new reactant, a whole new experimental set-up has to be developed. In most cases already described, the limiting step is the insertion of platinum in the Si-H bond, leading to an apparent rate of reaction independent of double bond concentration ... 

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