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Unlike CH bonds in hydrocarbon chemistry, the SiH bond in hydrosilanes may be viewed as a functional group. However, transformations of SiH to other Si-element bonds usually require a catalyst. Typical coreactants are HE1 species and if E1 represents another silicon unit, then homodehydrocoupling occurs to give silicon oligomers and polymers with H2 as the only by-product. Titanium triad complexes are particularly effective for this transformation. Silicon analogs of substituted ethanes, propanes and butanes can be formed through the reaction of secondary silanes such as PhMeSiH2 in the presence of the combination, Cp2MCl2 (M = Ti, Zr, Hf) and n-BuLi. With the availability of this simple dehydrogenative coupling reaction, the chemistry of short chains can be studied and developed. Examples include the removal of phenyl groups in H(PhMeSi)xH with l to x equivalents of triflic acid to give the corresponding silyl triflates, H[(Ph)x-y(OTf)ySixMex]H. Replacement of the triflate group by reaction with a number of nucleophiles may then take place to provide new oligomers. Oligomers with fluorosilane end groups have also been prepared through reaction with CuF2 or CuCl2/KF/KI.
Unlike CH bonds in hydrocarbon chemistry, the SiH bond in hydrosilanes may be viewed as a functional group. However, transformations of SiH to other Si-element bonds usually require a catalyst. Typical coreactants are HE1 species and if E1 represents another silicon unit, then homodehydrocoupling occurs to give silicon oligomers and polymers with H2 as the only by-product. Titanium triad complexes are particularly effective for this transformation. Silicon analogs of substituted ethanes, propanes and butanes can be formed through the reaction of secondary silanes such as PhMeSiH2 in the presence of the combination, Cp2MCl2 (M = Ti, Zr, Hf) and n-BuLi. With the availability of this simple dehydrogenative coupling reaction, the chemistry of short chains can be studied and developed. Examples include the removal of phenyl groups in H(PhMeSi)xH with l to x equivalents of triflic acid to give the corresponding silyl triflates, H[(Ph)x-y(OTf)ySixMex]H. Replacement of the triflate group by reaction with a number of nucleophiles may then take place to provide new oligomers. Oligomers with fluorosilane end groups have also been prepared through reaction with CuF2 or CuCl2/KF/KI.
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Aggregation-Induced Emission: Fundamentalspp.1-37, (2013)
Chemical Reviewsno. 2 (2011): 863-1071
ChemInformno. 33 (2010)
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