کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1326110 | 1499953 | 2005 | 10 صفحه PDF | دانلود رایگان |
1,3-Bis(3-butylimidazolium-1-yl)benzene diiodide (1) was reacted with Li(2,2,6,6-tetramethylpiperidine) yielding the free bis-carbene, 1,3-bis(3-butylimidazol-2-ylidene-1-yl)benzene (3), which has been spectroscopically characterized. Combining the free bis-carbene with [Rh(COD)Cl]2 yielded the corresponding di-Rh bis(N-heterocyclic carbene) complex (4) that was structurally characterized. The di-Rh bis-carbene complex was found to exhibit complex solution 13C and 1H NMR spectra that have been assigned as a mixture of diastereomers. The crystal structure of the di-Rh bis-carbene compound 4 was composed of a pair of enantiomeric atropisomers. The diastereomeric atropisomers were assigned as the source of the spectral complexities. The di-Rh di-carbene complex 4 and the CCC–NHC Rh pincer complex 2 were applied as catalysts in hydrosilylation reactions of terminal and internal alkynes. Both catalysts are highly active, regioselective, stereoselective, and chemoselective: terminal alkynes give predominantly the β-(Z) isomer and internal alkynes afford the β-(E) isomer in chloroform or benzene. One of the strongest attributes of the catalyst systems is that the results were achieved without exclusion of air and without purification of commercially available reagents.
A new di-Rh bis-carbene complex was found to be an efficient catalyst for hydrosilylation of alkynes without exclusion of air or water. Its catalytic effectiveness was compared to a CCC–NHC Rh pincer congener.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 690, Issues 24–25, 1 December 2005, Pages 5938–5947