Open AccessPyridine-Based PCP-Ruthenium Complexes: Unusual Structures and Metal–Ligand Cooperation
Author(s) -
Shan Tang,
Niklas von Wolff,
Yael DiskinPosner,
Gregory Leitus,
Yehoshoa BenDavid,
David Milstein
Publication year - 2019
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.9b02669
Subject(s) - chemistry , pincer movement , deprotonation , ruthenium , pyridine , aromatization , ligand (biochemistry) , reactivity (psychology) , pincer ligand , combinatorial chemistry , carbenoid , photochemistry , stereochemistry , medicinal chemistry , catalysis , organic chemistry , rhodium , biochemistry , receptor , medicine , ion , alternative medicine , pathology
Metal-ligand cooperation (MLC) by dearomatization/aromatization provides a unique way for bond activation, which has led to the discovery of various acceptorless dehydrogenative coupling reactions. However, most of the studies are based on pincer complexes with a central nitrogen donor. Aiming at exploration of the possibility of MLC by PCP-type pincer complexes, we report herein the synthesis, characterization, structure, and reactivity of pyridine-based PCP-Ru complexes. X-ray structures and DFT calculations indicate a carbenoid character of quaternized pyridine-based PCP-Ru complexes. These complexes undergo dearomatization by direct deprotonation, and the dearomatized complex can react with hydrogen, alcohols, or nitriles to regain aromatization via MLC.
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