Rotational Barriers of Substituted BIPHEP Ligands: A Comparative Experimental and Theoretical Study
- 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 kJmol(-1) and were found to be in excellent agreement with the calculated data. The root-mean-square deviations are 7.3 kJmol(-1) for the B3LYP functional and 11.3 kJmol(-1) for the M06-2X method.
| Author details: | Golo Storch, Frank Maier, Pablo WessigORCiDGND, Oliver Trapp |
|---|---|
| DOI: | https://doi.org/10.1002/ejoc.201600836 |
| ISSN: | 1434-193X |
| ISSN: | 1099-0690 |
| Title of parent work (English): | European journal of organic chemistry |
| Publisher: | Wiley-VCH |
| Place of publishing: | Weinheim |
| Publication type: | Article |
| Language: | English |
| Year of first publication: | 2016 |
| Publication year: | 2016 |
| Release date: | 2020/03/22 |
| Tag: | Biaryls; Density functional calculations; Enantioselectivity; Liquid chromatography; P ligands; Rotational barriers |
| Volume: | 22 |
| Number of pages: | 4 |
| First page: | 5123 |
| Last Page: | 5126 |
| Funding institution: | European Research Council (ERC) [258740]; German Fonds der Chemischen Industrie |
| Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
| Peer review: | Referiert |
