Coordination variability of Cu super(I) in multidonor heterocyclic thioamides: synthesis, crystal structures, luminescent properties and ESI-mass studies of complexes

The chemistry of copper(i) with scarcely investigated heterocyclic thioamides, particularly 2,4,6-trimercaptotriazine, purine-6-thione, 2,4-dithiouracil, 2-thiouracil and pyrimidine-2-thione is described. The interaction of 2,4,6-trimercaptotriazine (tmtH sub(3)) with [Cu(CH sub(3)COO)(PPh sub(3)) s...

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Bibliographic Details
Published in:RSC advances 2014-07, Vol.4 (58), p.30511-30522
Main Authors: Lobana, Tarlok S, Sandhu, Amanpreet K, Sultana, Razia, Castineiras, Alfonso, Butcher, Ray J, Jasinski, Jerry P
Format: Article
Language:English
Subjects:
Bands
Bonding
Chlorides
Crystal structure
Isomers
Luminescence
Optical properties
Synthesis
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Summary:The chemistry of copper(i) with scarcely investigated heterocyclic thioamides, particularly 2,4,6-trimercaptotriazine, purine-6-thione, 2,4-dithiouracil, 2-thiouracil and pyrimidine-2-thione is described. The interaction of 2,4,6-trimercaptotriazine (tmtH sub(3)) with [Cu(CH sub(3)COO)(PPh sub(3)) sub(2)] resulted in a pair of bond isomers: [Cu( Kappa super(1)N-tmtH sub(2))(PPh sub(3)) sub(2)] (6a), [Cu( Kappa super(1)N, Kappa super(1)S-tmtH sub(2))(PPh sub(3)) sub(2)] (6b); with copper(i) bromide and PPh sub(3), it formed a trinuclear complex, [Cu sub(3)Br sub(2)( Kappa super(1)N, Kappa super(1)S, mu -S-tmtH sub(2))(PPh sub(3)) sub(6)] (7) with anionic tmtH sub(2) super(-). The 2,4-dithiouracil with copper(i) halides (CuCl, CuBr) and PPh sub(3) yielded dinuclear complexes: [Cu sub(2)( mu -Cl)( Kappa super(1)S, Kappa super(1)S-dtucH)(PPh sub(3)) sub(4)] (4) and [Cu sub(2)( mu -Br)( Kappa super(1)S, Kappa super(1)S-dtucH)(PPh sub(3)) sub(4)] (5) with unusual eight-membered metallacyclic rings. Pyrimidine-2-thione (pymSH) is an N,S-chelated anion in a mononuclear complex, [Cu( Kappa super(1)N, Kappa super(1)S-pymS)(PPh sub(3)) sub(2)] (1), whereas 2-thiouracil (tucH sub(2)) with copper(i) chloride and PPh sub(3) yielded a tetrahedral complex, [CuCl( Kappa super(1)S-tucH sub(2))(PPh sub(3)) sub(2)] (3). Purine-6-thione (purSH sub(2)) coordinated to Cu super(I) in two different modes yielding mono- and di-nuclear complexes, [Cu( Kappa super(1)N, Kappa super(1)S-purS)(PPh sub(3)) sub(2)].CH sub(3)OH (2a) and [Cu sub(2)( Kappa super(1)N, mu -S-purS) sub(2)(PPh sub(3)) sub(2)] (2b). The existence of bond isomers (6a and 6b), synthesis of novel dinuclear (4 and 5) and rare trinuclear (7) complexes with unusual bonding patterns are the novel features of the present study. Complexes show intense emission bands in the 380-530 nm region with lambda sub(em) at 490 to 495 nm.
ISSN:2046-2069
DOI:10.1039/c4ra02748e