Rotational Barriers of Substituted BIPHEP Ligands: A Comparative Experimental and Theoretical Study

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• 作者：Golo Storch ; Frank Maier ; Pablo Wessig and Oliver Trapp
• 刊名：European Journal of Organic Chemistry
• 出版年：2016
• 出版时间：October 2016
• 年：2016
• 卷：2016
• 期：30
• 页码：5123-5126
• 全文大小：682K
• ISSN：1099-0690

文摘

The interconversion barriers of 14 different 3,3′- and 5,5′-disubstituted tropos BIPHEP [2,2′-bis(diphenylphosphino)-1,1′-biphenyl] and BIPHEP(O) [2,2′-bis(diphenylphosphoryl)-1,1′-biphenyl] ligands were investigated by enantioselective dynamic high performance liquid chromatography (DHPLC) and DFT calculations using the B3LYP/6-31G* and M06-2X/6-31G* levels of theory. The experimentally determined enantiomerization barriers varied from 86.8 to 101.4 kJ mol^–1 and were found to be in excellent agreement with the calculated data. The root-mean-square deviations are 7.3 kJ mol^–1 for the B3LYP functional and 11.3 kJ mol^–1 for the M06-2X method.