Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 51, Pages 16748-16753Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201810511
Keywords
carbon monoxide; organometallic complexes; P ligands; proton transfer; thorium
Categories
Funding
- U.S. Department of Energy, Office of Science, Early Career Research Program [DE-SC-0014174]
- HPCs CALcul en Midi-Pyrenees (CALMIP-EOS) [1415]
Ask authors/readers for more resources
We report intramolecular proton transfer reactions to functionalize carbon monoxide and tert-butyl nitrile from a bis(phosphido) thorium complex. The reaction of (C5Me5)(2)Th[PH(Mes)](2), Mes = 2,4,6-Me3C6H2, with 1 atm of CO yields (C5Me5)(2)Th(kappa(2)-(O,O)-OCH(2)PMes-C(O)PMes), in which one CO molecule is inserted into each thorium-phosphorus bond. Concomitant transfer of two protons, formerly coordinated to phosphorus, are now bound to one of the carbon atoms from one of the inserted CO molecules. DFT calculations were employed to determine the lowest energy pathway. With tert-butyl nitrile, (BuCN)-Bu-t, only one nitrile inserts into a thorium-phosphorus bond, but the proton is transferred to nitrogen with one phosphido remaining unperturbed affording (C5Me5)(2)Th[PH(Mes)][kappa(2)-(P,N)-N(H)C(CMe3)P(Mes)]. Surprisingly, reaction of this compound with KN(SiMe3)(2) removes the proton bound to nitrogen, not phosphorus.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available