TY - JOUR
T1 - Pyridine-Based PCP-Ruthenium Complexes
T2 - Unusual Structures and Metal-Ligand Cooperation
AU - Tang, Shan
AU - Von Wolff, Niklas
AU - Diskin-Posner, Yael
AU - Leitus, Gregory
AU - Ben-David, Yehoshoa
AU - Milstein, David
PY - 2019/4/19
Y1 - 2019/4/19
N2 - 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.
AB - 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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U2 - 10.1021/jacs.9b02669
DO - 10.1021/jacs.9b02669
M3 - Article
C2 - 31017407
AN - SCOPUS:85065466240
VL - 141
SP - 7554
EP - 7561
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 18
ER -