Functionalization of Carbon Monoxide and tert-Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex
Dr. Sean P. Vilanova
Department of Chemistry, University of Missouri, Columbia, MO, 65211 USA
Search for more papers by this authorDr. Iker del Rosal
Universite de Toulouse, CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077 Toulouse, France
Search for more papers by this authorMichael L. Tarlton
Department of Chemistry, University of Missouri, Columbia, MO, 65211 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Laurent Maron
Universite de Toulouse, CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077 Toulouse, France
Search for more papers by this authorCorresponding Author
Dr. Justin R. Walensky
Department of Chemistry, University of Missouri, Columbia, MO, 65211 USA
Search for more papers by this authorDr. Sean P. Vilanova
Department of Chemistry, University of Missouri, Columbia, MO, 65211 USA
Search for more papers by this authorDr. Iker del Rosal
Universite de Toulouse, CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077 Toulouse, France
Search for more papers by this authorMichael L. Tarlton
Department of Chemistry, University of Missouri, Columbia, MO, 65211 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Laurent Maron
Universite de Toulouse, CNRS, INSA, UPS, CNRS, UMR, UMR 5215, LPCNO, 135 Avenue de Rangueil, 31077 Toulouse, France
Search for more papers by this authorCorresponding Author
Dr. Justin R. Walensky
Department of Chemistry, University of Missouri, Columbia, MO, 65211 USA
Search for more papers by this authorGraphical Abstract
Building on CO: A primary bis(phosphido) complex gives both hydrogen atoms from each phosphorus center to a single carbon atom when treated with carbon monoxide. This is a rare example of the conversion of CO into a formyl-like species through intramolecular proton transfer.
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.
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