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Well‐Defined Models for the Elusive Dinuclear Intermediates of the Pauson–Khand Reaction
Author(s) -
Hartline Douglas R.,
Zeller Matthias,
Uyeda Christopher
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201601784
Subject(s) - metallacycle , chemistry , pauson–khand reaction , ligand (biochemistry) , alkyne , combinatorial chemistry , reaction intermediate , reaction mechanism , diimine , defeasible estate , stereochemistry , organic chemistry , catalysis , computer science , receptor , physics , x ray crystallography , biochemistry , intramolecular force , diffraction , optics , artificial intelligence
The mechanism of the Pauson–Khand reaction has attracted significant interest due to the unusual dinuclear nature of the Co 2 (CO) x active site. Experimental and computational data have indicated that the intermediates following the initial Co 2 (CO) 6 (alkyne) complex are thermodynamically unstable and do not build up in appreciable concentrations during the course of the reaction. As a consequence, the key steps that control the scope of viable substrates and various aspects of selectivity have remained largely uncharacterized. Herein, a direct experimental investigation of the dinuclear metallacycle‐forming step of the Pauson–Khand reaction is reported. These studies capitalize on well‐defined d 9 –d 9 dinickel complexes supported by a naphthyridine–diimine (NDI) pincer ligand as functional surrogates of Co 2 (CO) 8 .