G. Storch, F. Maier, P. Wessig, O. Trapp
Rotational Barriers of substituted Biphep Ligands – A Comparative Experimental and Theoretical Study
Eur. J. Org. Chem. 2016, 5123-5126
DOI: 10.1002/ejoc.201600836
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.
Zurück zur Übersicht »