Back to Search
Start Over
Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex.
- Source :
-
Angewandte Chemie . Dec2018, Vol. 130 Issue 51, p16990-16995. 6p. - Publication Year :
- 2018
-
Abstract
- We report intramolecular proton transfer reactions to functionalize carbon monoxide and tert‐butyl nitrile from a bis(phosphido) thorium complex. The reaction of (C5Me5)2Th[PH(Mes)]2, Mes=2,4,6‐Me3C6H2, with 1 atm of CO yields (C5Me5)2Th(κ2‐(O,O)‐OCH2PMes‐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, tBuCN, only one nitrile inserts into a thorium–phosphorus bond, but the proton is transferred to nitrogen with one phosphido remaining unperturbed affording (C5Me5)2Th[PH(Mes)][κ2‐(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. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00448249
- Volume :
- 130
- Issue :
- 51
- Database :
- Academic Search Index
- Journal :
- Angewandte Chemie
- Publication Type :
- Academic Journal
- Accession number :
- 133500266
- Full Text :
- https://doi.org/10.1002/ange.201810511