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
N1 - Funding Information:
This research was supported by the European Research Council (ERC AdG 692775). D.M. holds the Israel Matz Professorial Chair of Organic Chemistry. S.T. is thankful to the Israel Planning and Budgeting Committee (PBC) for a postdoctoral fellowship. N.v.W. is supported by the Foreign Postdoctoral Fellowship Program of the Israel Academy of Sciences and Humanities.
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 -