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Chemistry of Heterocyclic 2‐Thiones: In Situ Generation of 3‐(2‐Thiazolin‐2‐yl)thiazolidine‐2‐thione and 1,1′‐Dimethyl‐2,2′‐diimidazolyl Sulfide and Their Coordination to Cu I and Cu II
Author(s) -
Lobana Tarlok S.,
Sultana Razia,
Butcher Ray J.,
Castineiras Alfonso,
Akitsu Takashiro,
Fernandez Francisco J.,
Vega M. Cristina
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300676
Subject(s) - chemistry , thiazolidine , bromide , medicinal chemistry , ligand (biochemistry) , copper , bond cleavage , reactivity (psychology) , chloride , chelation , coordination complex , metal , stereochemistry , inorganic chemistry , organic chemistry , catalysis , pathology , medicine , biochemistry , receptor , alternative medicine
The chemical reactivity of copper(I) chloride/copper(I) bromide, [Cu I (NCCH 3 ) 4 ](BF 4 ), and copper(II) nitrate towards a series of heterocyclic‐2‐thiones under aerobic conditions is described. Thiazolidine‐2‐thione (NC 3 H 5 S 2 ) in CH 3 CN in the presence of copper(I) chloride/bromide and [Cu I (NCCH 3 ) 4 ](BF 4 ) was transformed into 3‐(2‐thiazolin‐2‐yl)thiazolidine‐2‐thione (C 3 H 4 S 2 N‐C 3 H 4 SN) through C–S bond cleavage and the formation of a C–N bond between two heterocyclic rings. This new thio ligand (C 3 H 4 S 2 N‐C 3 H 4 SN) chelates to Cu I through N,S‐donor atoms, and the third site is occupied by the halogen atoms (Cl, Br), which leads to the formation of three‐coordinate Cu I complexes, [Cu I X(κ 2 ‐ N , S ‐C 3 H 4 S 2 N‐C 3 H 4 SN)] [X = Cl ( 1 ), Br ( 2 )], and a four‐coordinate N,S‐chelated complex, [Cu I (κ 2 ‐ N , S ‐C 3 H 4 S 2 N‐C 3 H 4 SN) 2 ](BF 4 ) ( 3 ), is obtained in the presence of BF 4 – . In each case, the formation of CuSO 4 · 5H 2 O was also observed. Upon reaction of 1‐methylimidazoline‐2‐thione (N 2 C 4 H 6 S) with [Cu I (NCCH 3 ) 4 ](BF 4 ) or copper(II) nitrate in CH 3 CN or CH 3 CN/MeOH, respectively, the thio ligand is converted into 1,1′‐dimethyl‐2,2′‐diimidazolyl sulfide (N 2 C 4 H 5 ) 2 S (a thioether), which prefers to bind to Cu II (in situ formed) to yield six‐coordinate N,N‐chelated octahedral complexes, namely, {Cu II [κ 2 ‐ N , N ‐(N 2 C 4 H 5 ) 2 S] 2 (κ 1 ‐OH 2 ) 2 }X 2 [X = BF 4 ( 6 ), NO 3 ( 7 )], with water in the axial positions. The transformation of the thio ligand into 1,1′‐dimethyl‐2,2′‐diimidazolyl sulfide is also observed in its copper(I) chloride reaction in acetonitrile, which yields an N,N‐chelated chloro‐bridged dimer, {Cu II 2 [κ 2 ‐ N , N ‐(N 2 C 4 H 5 ) 2 S] 2 (μ‐Cl) 2 Cl 2 } ( 5 ). Reaction of copper(I) iodide with thiazolidine‐2‐thione and 1‐methylimidazolidine‐2‐thione (N 2 C 4 H 8 S) in acetonitrile yields an iodo‐bridged dimer, [Cu 2 (κ 1 ‐ S ‐NC 3 H 5 S 2 ) 4 (μ‐I) 2 ] ( 4 ), and a novel polymer, [Cu 4 (μ 3 ‐I) 2 (μ‐I) 2 (μ‐ S ‐N 2 C 4 H 8 S) 2 (κ 1 ‐ S ‐N 2 C 4 H 8 S)] n ( 8 ), respectively.