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Ruthenium‐Carbon(Aryl) Bond Cleavage and Change in the Ligand Coordination Mode in a Four‐Membered Ortho‐Metalated Ruthenium(II) Organometallics Promoted by Thiolato Ligands
Author(s) -
Ghosh Mrinal K.,
Mandal Suman,
Islam Anikul,
Mohapatra Sudip,
Chattopadhyay Swarup
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201701046
Subject(s) - chemistry , ruthenium , medicinal chemistry , dichloromethane , aryl , comproportionation , ligand (biochemistry) , tetrahydrofuran , stereochemistry , imine , bond cleavage , electrochemistry , catalysis , organic chemistry , biochemistry , alkyl , receptor , electrode , solvent
The reaction of Ru( η 2 ‐RL)(PPh 3 ) 2 (CO)Cl [ η 2 ‐RL is C 6 H 2 O‐2‐CHNHC 6 H 4 R( p )‐3‐Me‐5 and R=Me, OMe, Cl] with excess sodium p‐ chlorothiophenolate ( p ‐ClC 6 H 4 SNa) in dichloromethane–tetrahydrofuran medium afforded the binuclear complexes of the type [Ru(PPh 3 )( η 2 ‐RL)(CO)( p ‐ClC 6 H 4 S)] 2 [ η 2 ‐RL is C 6 H 3 O‐2‐CHNC 6 H 4 R( p )‐3‐Me‐5] in excellent yield. The binding of the thiolato ligands is attended with the cleavage of the Ru–C(aryl) and Ru–Cl bonds in Ru( η 2 ‐RL)(PPh 3 ) 2 (CO)Cl and the RL ligands are now coordinated with the metals in [Ru(PPh 3 )( η 2 ‐RL)(CO)( p ‐ClC 6 H 4 S)] 2 via the imine nitrogen and the phenolato oxygen atoms. The CO ligand in [Ru(PPh 3 )( η 2 ‐RL)(CO)( p ‐ClC 6 H 4 S)] 2 remains trans to the phenolato function as in Ru( η 2 ‐RL)(PPh 3 ) 2 (CO)Cl. The spectral (UV‐vis, IR, NMR, mass) and electrochemical data of the complexes are included. In dichloromethane solution the complexes display two successive one‐electron oxidation waves. The comproportionation constants ( K C ) as calculated by the ▵ E 1/2 values of the complexes are in the order of 10 5 indicating that the two metal centers in [Ru(PPh 3 )( η 2 ‐RL)(CO)( p ‐ClC 6 H 4 S)] 2 are only weakly coupled by the bridging thiolato liagnds. Structure determinations of [Ru(PPh 3 )( η 2 ‐RL)(CO)( p ‐ClC 6 H 4 S)] 2 (R=Me, OMe) have revealed a distorted octahedral RuCONPS 2 coordination sphere with the pairs (P, S), (C, O), and (N, S) defining the three trans directions. The Ru⋅⋅⋅⋅Ru distances in the complexes are clearly outside of the range for a Ru‐Ru single bond. The electronic structures and the absorption spectra of the complexes are also scrutinized by the density functional theory (DFT) and Time‐dependent DFT analysis.