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Functionalization of Carbon Monoxide and tert ‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex
Author(s) -
Vilanova Sean P.,
del Rosal Iker,
Tarlton Michael L.,
Maron Laurent,
Walensky Justin R.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201810511
Subject(s) - intramolecular force , chemistry , nitrile , carbon monoxide , medicinal chemistry , thorium , molecule , proton , phosphorus , nitrogen , photochemistry , organic chemistry , catalysis , materials science , physics , uranium , quantum mechanics , metallurgy
Abstract We report intramolecular proton transfer reactions to functionalize carbon monoxide and tert ‐butyl nitrile from a bis(phosphido) thorium complex. The reaction of (C 5 Me 5 ) 2 Th[PH(Mes)] 2 , Mes=2,4,6‐Me 3 C 6 H 2 , with 1 atm of CO yields (C 5 Me 5 ) 2 Th( κ 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, t BuCN, only one nitrile inserts into a thorium–phosphorus bond, but the proton is transferred to nitrogen with one phosphido remaining unperturbed affording (C 5 Me 5 ) 2 Th[PH(Mes)][ κ 2 ‐(P,N)‐N(H)C(CMe 3 )P(Mes)]. Surprisingly, reaction of this compound with KN(SiMe 3 ) 2 removes the proton bound to nitrogen, not phosphorus.