The reactions of Rh₂(CO)₄Cl₂ with 1,5-cyclooctadiene and tetramethylallene. A combined in-situ vibrational spectroscopies, spectral reconstruction and DFT study

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• 作者：Feng Gao ; Chuanzhao Li ; Effendi Widjaja ; Chacko Jacob ; Marc Garl
• 关键词：Rhodium complexes ; Tetramethylallene ; In-situ spectroscopies ; BTEM ; DFT
• 刊名：Journal of Organometallic Chemistry
• 出版年：2010
• 出版时间：15 October 2010
• 年：2010
• 卷：695
• 期：22
• 页码：2394-2400
• 全文大小：509 K

文摘

Reactions of Rh₂(CO)₄Cl₂ with 1,5-cyclooctadiene (COD) and tetramethylallene (TMA) were performed separately in anhydrous hexane under argon atmosphere. Multiple perturbations of Rh₂(CO)₄Cl₂, COD and TMA were also performed during the reactions. These two reactions were monitored by in-situ FTIR (FIR and MIR) and/or Raman spectroscopies and the collected spectra were further analyzed with BTEM family of algorithms. DFT calculations were performed to identify the organometallic species present. The known diene complex Rh₂(CO)₂Cl₂(η⁴-C₈H₁₂) and a new allene complex Rh₂(CO)₃Cl₂(η²-C₇H₁₂) were formed as the two primary organo-rhodium products. Their pure component spectra were reconstructed in the three characteristic regions of 200–680, 800–1360, and 1500–2200 cm⁻¹. Their relative concentrations were also obtained by the least square fitting of the carbonyl region 1500-2200 cm⁻¹. The present contribution shows the usefulness of combining in-situ spectroscopic measurements, BTEM analysis and DFT spectral prediction in order to analyze organometallic reactions at high dilution and identify the reaction products.