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Synthesis and Structural Characterization of Mixed‐Ligand Oxorhenium(V) Complexes Containing Bidentate Dithioethers and Monothiolato Ligands
Author(s) -
Reisgys Martina,
Spies Hartmut,
Johannesn Bernd,
Pietzsch HansJergen,
Leibnitz Peter
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971300927
Subject(s) - chemistry , denticity , ligand (biochemistry) , octahedron , medicinal chemistry , coordination sphere , homoleptic , hydrobromic acid , protonation , crystal structure , bromide , acetic acid , stereochemistry , chloride , crystallography , inorganic chemistry , ion , metal , organic chemistry , biochemistry , receptor
Neutral oxorhenium(V) complexes with dithioether ligands of the general formula [ReOX 3 (RS[CH 2 ] 2 SR)], × = Cl, Br, R = n Bu, Et, Bzl were synthesized. Ammonium perrhenate reacts in concentrated hydrochloric acid with dithiaalkanes (RS[CH 2 ] 2 SR, R = n Bu, Et, Bz) dissolved in glacial acetic acid to give octahedral complexes of the type [ReOCl 3 (RS[CH 2 ] 2 SR)] ( 1a – c ). In concentrated hydrobromic acid, n Bu–S(Ch 2 ) 2 S– n Bu leads to the corresponding tribromo complexes ( 2 ). The X‐ray structure of shows a distorted octahedron with facial coordination of the bromide ligands. The sulfur atoms are cis coordinated to the terminal oxygen. Dissolution o f 1a (R = n Bu) in methanol leads to the substitution of the chloride trans to the oxo ligand by a meth oxy group. The resultant complex [ReOCl 2 (MeO) ( n Bu–S[CHL2] 2 S– n Bu)] ( 3 ) is stable and can be isolated from methanolic solution, but changes to the μ‐oxo‐bridged dirhenium complex μ‐oxobis[dichloro(5,6‐dithiadidodecane)oxorhenium(V)] ( 4 ) when dissolved in other organic solvents. 1a reacts with an excess of benzenethiol by substitution of two chlorides to give the mixed‐ligand complex bis(benzenethiolate)chloro(5,8‐dithiadodecane)oxorhenium(V) ( 5a ). The related 4‐methylbenzenethiolato complex 5b was synthesized starting from the μ‐oxo complex 4 . X‐ray crystal structure determination of 5b shows the equatorial arrangement of the sulfur atoms. The trans position to the oxygen atom is occupied by a chloride ion.