Experimental and Theoretical Study of Molecular Response of Amine Bases in Organic Solvents
Reorientational correlation times of various amine bases (viz., pyridine, 2,6-lutidene, 2,2,6,6-tetramethylpiperidine) and organic solvents (dichloromethane, toluene) were determined by solution-state NMR relaxation time measurements and compared with predictions from molecular dynamics (MD) simulations. The bases and solvents are reagents in complex reactions involving Frustrated Lewis Pairs (FLP), which display remarkable catalytic activity in metal-free H2 scission. The comparison of measured and simulated correlation times is a key test of the ability of recent MD and quantum electronic structure calculations to elucidate the mechanism of FLP activity. Correla- tion times were found to be in the range 1.4-3.4 ps (NMR) and 1.23-5.28 ps (MD) for the amines, and 0.9-2.3 ps (NMR) and 0.2-1.7 ps (MD) for the solvent molecules. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacic Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1134514
- Report Number(s):
- PNNL-SA-100585; KC0302010
- Journal Information:
- Journal of Physical Chemistry B, 118(18):4883-4888, Journal Name: Journal of Physical Chemistry B, 118(18):4883-4888
- Country of Publication:
- United States
- Language:
- English
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