Strong 蟺-Acceptor Ligands in Rhodium-Catalyzed Hydroformylation of Ethene and 1-Octene: Operando Catalysis

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• 作者：Olivier Diebolt ; Hugo Tricas ; Zoraida Freixa ; Piet W. N. M. van Leeuwen
• 刊名：ACS Catalysis
• 出版年：2013
• 出版时间：February 1, 2013
• 年：2013
• 卷：3
• 期：2
• 页码：128-137
• 全文大小：652K
• 年卷期：v.3,no.2(February 1, 2013)
• ISSN：2155-5435

文摘

Strong 蟺-acceptor N-pyrrolylphosphoramidite and pyrrolylphosphine mono- and bidentante ligands were applied in ethene hydroformylation using a stoichiometric gas mixture CO/H₂/ethene 1:1:1. Very fast reactions (TOF up to 29.5 脳 10³ mol mol^鈥? h^鈥?, 13-fold faster than triphenylphosphine) and excellent selectivities were obtained. The pyrrolylphosphine derivatives of SPANphos and Xantphos, pySPAN and pyXANT, were used in 1-octene hydroformylation. The electronic character of these ligands improved both activities and regioselectivities compared with the phenyl-substituted ligands. HPNMR and HPIR showed that both pySPAN and pyXANT favor the formation of bisequatorial [RhH(CO)₂(ligand)] complexes under catalytic conditions.

Keywords:

in situ spectroscopy; 蟺-accepting phosphorus ligands; rhodium; ethene; hydroformylation