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Cleavage of Ru-C(aryl) bond of a four-membered ortho-metalated ruthenium(II) organometallics by mercaptopyrimidine and pyridine-2,6-dicarboxylate ligands: spectroscopic, structural and computational studies

Ghosh, Mrinal Kanti, Mallick, Suman, Islam, Anikul, Mohapatra, Sudip and Chattopadhyay, Swarup 2016, Cleavage of Ru-C(aryl) bond of a four-membered ortho-metalated ruthenium(II) organometallics by mercaptopyrimidine and pyridine-2,6-dicarboxylate ligands: spectroscopic, structural and computational studies, Polyhedron, vol. 104, pp. 73-79, doi: 10.1016/j.poly.2015.11.040.

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Title Cleavage of Ru-C(aryl) bond of a four-membered ortho-metalated ruthenium(II) organometallics by mercaptopyrimidine and pyridine-2,6-dicarboxylate ligands: spectroscopic, structural and computational studies
Author(s) Ghosh, Mrinal Kanti
Mallick, Suman
Islam, Anikul
Mohapatra, Sudip
Chattopadhyay, Swarup
Journal name Polyhedron
Volume number 104
Start page 73
End page 79
Total pages 7
Publisher Elsevier
Place of publication Amsterdam, The Netherlands
Publication date 2016-01-28
ISSN 0277-5387
Keyword(s) ruthenium complex
mercaptopyrimidine
pyridine-2,6-dicarboxylate
density functional theory
cleavage of Ru-(aryl) bond
Summary The heterogeneous phase reaction of Ru(η2-RL)(PPh3)2(CO)Cl (1) with 2-mercaptopyrimidine(pymSH) and pyridine-2,6-dicarboxylate(dipic) ligands afforded the complexes of the type Ru(PPh3)(CO)(pymS)2 (2) and Ru(PPh3)2(CO)(dipic) (3) in excellent yield respectively. The chelation of pymS/dipic is attended with the cleavage of Ru-O, Ru-Cl and Ru-C(aryl) bonds and the RL ligand is no longer coordinated with the metal center in the products. The spectral (UV-Vis, IR, 1H NMR) and electrochemical data of the complexes are included. In dichloromethane solution both 2 and 3 display one quasi-reversible RuIII/RuII cyclic voltammetric response with E1/2 in the range 1.15-1.50 V vs Ag/AgCl. Structure determinations of 2 and the solvate 3·CH3CN have revealed distorted octahedral RuCN2S2P coordination sphere for 2 and RuCNO2P2 coordination sphere for 3·CH3CN. For 2 the pairs (P, N), (S, S) and (C, N) define the three trans directions whereas for 3·CH3CN those pairs are (P, P), (C, N) and (O, O). The electronic structures and the absorption spectra of 2 and 3 are also scrutinized by the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) analysis.
Language eng
DOI 10.1016/j.poly.2015.11.040
Field of Research 030199 Analytical Chemistry not elsewhere classified
0302 Inorganic Chemistry
0399 Other Chemical Sciences
Socio Economic Objective 970103 Expanding Knowledge in the Chemical Sciences
HERDC Research category C1.1 Refereed article in a scholarly journal
ERA Research output type C Journal article
Copyright notice ©2015, Elsevier
Persistent URL http://hdl.handle.net/10536/DRO/DU:30088470

Document type: Journal Article
Collection: School of Life and Environmental Sciences
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