New Square-Planar Bis(Dithiolene) Complexes: Synthesis, Crystallography, and Properties of [Bu4N][MIII(btdt)2] (M = Cu, Au) and [Bu4N]2[PtII(btdt)2] ({btdt}2– =2,1,3-Benzenethiadiazole-5,6-dithiolate)

Ramababu Bolligarla; Samar K. Das

doi:10.1071/CH11075

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New Square-Planar Bis(Dithiolene) Complexes: Synthesis, Crystallography, and Properties of [Bu₄N][M^III(btdt)₂] (M = Cu, Au) and [Bu₄N]₂[Pt^II(btdt)₂] ({btdt}^2– =2,1,3-Benzenethiadiazole-5,6-dithiolate)

Ramababu Bolligarla ^A and Samar K. Das ^A ^B

+ Author Affiliations

- Author Affiliations

^A School of Chemistry, University of Hyderabad, Hyderabad 500 046, India.

^B Corresponding author. Email: skdsc@uohyd.ernet.in

Australian Journal of Chemistry 64(5) 550-560 https://doi.org/10.1071/CH11075
Submitted: 15 February 2011 Accepted: 9 March 2011 Published: 30 May 2011

Abstract

The syntheses, crystal structures, and properties of three new coordination complexes [Bu₄N][M^III(btdt)₂] [M = Cu (1), Au (2)] and [Bu₄N]₂[Pt^II(btdt)₂] (3) ({btdt}^2– = 2,1,3-benzenethiadiazole-5,6-dithiolate) are described. Compounds 1–3 crystallize in a triclinic P-1, and monoclinic P2(1)/c and C2/c space groups, respectively. The {MS₄} chromophore lies in almost a square-planar coordination environment in complex 1, but has a slightly distorted square-planar geometry around the central metal ion in compounds 2 and 3. Interactions in the solid state have been studied by intermolecular contacts, in particular, compounds 2 and 3 have been characterized by SN and SS non-covalent interactions among dithiolate complexes, resulting in two- and one-dimensional supramolecular motifs, respectively. Complexes 1–3 show broad absorption bands in the visible region, with that of 3 being sensitive to solvent polarity. Complex 1 exhibits a very low reduction potential for a Cu^III-coordination complex, while the Pt^II complex 3 shows two irreversible oxidative responses at 0.45 V and 0.74 V versus Ag/AgCl, respectively.

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New Square-Planar Bis(Dithiolene) Complexes: Synthesis, Crystallography, and Properties of [Bu4N][MIII(btdt)2] (M = Cu, Au) and [Bu4N]2[PtII(btdt)2] ({btdt}2– =2,1,3-Benzenethiadiazole-5,6-dithiolate)

Abstract

References

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New Square-Planar Bis(Dithiolene) Complexes: Synthesis, Crystallography, and Properties of [Bu₄N][M^III(btdt)₂] (M = Cu, Au) and [Bu₄N]₂[Pt^II(btdt)₂] ({btdt}^2– =2,1,3-Benzenethiadiazole-5,6-dithiolate)