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Ligand Design for Site‐Selective Metal Coordination: Synthesis of Transition‐Metal Complexes with η 6 ‐Coordination of the Central Ring of Anthracene
Author(s) -
Karslyan Eduard E.,
Borissova Alexandra O.,
Perekalin Dmitry S.
Publication year - 2017
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.201700685
Subject(s) - ligand (biochemistry) , ring (chemistry) , chemistry , metal , transition metal , anthracene , coordination complex , stereochemistry , selectivity , molecular orbital , crystallography , photochemistry , molecule , organic chemistry , catalysis , biochemistry , receptor
A polycyclic aromatic ligand for site‐selective metal coordination was designed by using DFT calculations. The computational prediction was confirmed by experiments: 2,3,6,7‐tetramethoxy‐9,10‐dimethylanthracene initially reacts with [(C 5 H 5 )Ru(MeCN) 3 ]BF 4 to give the kinetic product with a [(C 5 H 5 )Ru] + fragment coordinated at the terminal ring, which is then transformed into the thermodynamic product with coordination through the central ring. These isomeric complexes have markedly different UV/Vis spectra, which was explained by analysis of the frontier orbitals. At the same time, the calculations suggest that electrostatic interactions are mainly responsible for the site selectivity of the coordination.