Hydrogen/Deuterium Exchange Reactions and Transfer Hydrogenations Catalyzed by [C5Me5Rh(olefin)2] Complexes: Conversion of Alkoxysilanes to Silyl Enolates
| Autor: | Christian P. Lenges, Peter S. White, Maurice Brookhart |
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| Rok vydání: | 1999 |
| Předmět: | |
| Zdroj: | Journal of the American Chemical Society. 121:4385-4396 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja984409o |
| Popis: | A series of [C5Me5Rh(CH2CHR)2] complexes (1a−e) have been prepared in which the olefin bears a bulky silyl substituent, R = (a) SiMe3, (b) SiMe2OEt, (c) Si(OiPr)3, (d) SiMe(OSiMe3)2, (e) SiPh2OiPr. The solid-state structure of 1c has been determined by X-ray crystallography. When complex 1a is heated (50 °C) in deuterated solvents (C6D6, C6D5CD3, C6D5Cl, or (CD3)2CO), deuterium is incorporated into the olefinic sites. Thermolysis at higher temperatures results in further H/D exchange and deuteration of both the SiMe3 and C5Me5 groups. Heating 1a in C6D6 with added substrates (aniline, MeOtBu, MeOSiMe3, Cp2Fe, cyclopentene, or EtOAc) results in deuteration of these substrates via shuttling of deuterium from C6D6 to the olefinic sites and then into certain sites of the substrates. Thermolysis of 1a in the presence of vinyltrimethylsilane at higher temperatures results in C−Si bond cleavage and generation of a silacyclopentadiene complex (6) whose structure was determined by X-ray analysis. Thermolysis of 1c... |
| Databáze: | OpenAIRE |
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