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Alkyne gem ‐Hydrogenation: Formation of Pianostool Ruthenium Carbene Complexes and Analysis of Their Chemical Character
Author(s) -
Biberger Tobias,
Gordon Christopher P.,
Leutzsch Markus,
Peil Sebastian,
Guthertz Alexandre,
Copéret Christophe,
Fürstner Alois
Publication year - 2019
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.201904255
Subject(s) - ruthenium , carbene , alkyne , chemistry , electrophile , reactivity (psychology) , metathesis , nuclear magnetic resonance spectroscopy , chemical shift , photochemistry , transition metal carbene complex , catalysis , stereochemistry , organic chemistry , polymer , polymerization , medicine , alternative medicine , pathology
Parahydrogen ( p ‐H 2 ) induced polarization (PHIP) NMR spectroscopy showed that [Cp X Ru] complexes with greatly different electronic properties invariably engage propargyl alcohol derivatives into gem ‐hydrogenation with formation of pianostool ruthenium carbenes; in so doing, less electron rich Cp X rings lower the barriers, stabilize the resulting complexes and hence provide opportunities for harnessing genuine carbene reactivity. The chemical character of the resulting ruthenium complexes was studied by DFT‐assisted analysis of the chemical shift tensors determined by solid‐state 13 C NMR spectroscopy. The combined experimental and computational data draw the portrait of a family of ruthenium carbenes that amalgamate purely electrophilic behavior with characteristics more befitting metathesis‐active Grubbs‐type catalysts.