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Experimental and computational studies on a new mixed ligand oxido –rhenium(V) compound
Author(s) -
Saha Pinki,
Naskar Jnan Prakash,
Majumder Smita,
Saha Baptu,
Ganguly Rakesh,
Bhattacharya Arnab,
Chowdhury Shubhamoy
Publication year - 2018
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201800033
Subject(s) - rhenium , chemistry , ligand (biochemistry) , denticity , density functional theory , crystallography , electrochemistry , moiety , redox , crystal structure , square pyramidal molecular geometry , stereochemistry , computational chemistry , inorganic chemistry , biochemistry , receptor , electrode
A mixed ligand oxido –rhenium(V) complex, [ReOS 3 (HL)]Cl.H 2 O ( 1p Cl.H 2 O), with 3‐thiopentane‐1,5‐dithiolato (S 3 ) as a tridentate ligand and imidazolidinethione (HL) as an ancillary monodentate sulfur donor co‐ligand, has been synthesized. 1p Cl.H 2 O has been characterized by spectral analyses. The X‐ray crystal structure of 1p Cl.H 2 O shows that the complex contains a distorted square‐pyramidal “ReOS 4 ” core. The structural parameters agree with our optimized structure of 1p + . Subsequently, the optimized structure was used to calculate systematically the relative stabilities of a sequence of oxido –Re(V) and the analogous oxido –Tc(V) complexes just by varying the donor sites (N, S, and O) on the tridentate ligand moiety in 1p + . Electrochemical studies on 1p Cl.H 2 O show an oxidative rhenium(VI)/ rhenium(V) couple at 1.561 V versus Ag/AgCl under controlled linear diffusion situation. Vibrational frequencies, electronic structures, and redox potential of 1p + have been calculated theoretically employing density functional theory (DFT) or time‐dependent‐DFT methods. The experimental findings are in excellent agreement with the computed results. The calculated redox potentials of the investigated oxido –Re(V) complexes and their oxido –Tc(V) counterparts are shown to correlate linearly with their respective chemical potential values.