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Palladium complexes of pyrrole-2-aldehyde thiosemicarbazone: Synthesis, structure and spectral properties

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Abstract

Reaction of pyrrole-2-aldehyde thiosemicarbazone (abbreviated as H 2 L, where H2 stands for the two potentially dissociable protons) with [Pd(PPh3)2Cl2] in ethanol in the presence of NEt3 afforded two complexes, [Pd(PPh3)(HLNS)Cl] and [Pd(PPh3)(LNNS)], where the thiosemicarbazone ligand is coordinated to the metal centre respectively as monoanionic N,S-donor (depicted by HLNS) and dianionic N,N,S-donor (depicted by LNNS). Similar reaction with Na2[PdCl4] afforded a bis-complex, [Pd(HLNS)2]. Crystal structures of all the three complexes have been determined. With reference to the structure of the uncoordinated thiosemicarbazone (H 2 L), the N,S-coordination mode observed in [Pd(PPh3)(HLNS)Cl] and [Pd(HLNS)2] is associated with a geometrical change around the imine bond. While the N,N,S-mode of binding observed in [Pd(PPh3)(LNNS)] takes place without any such geometrical change. All three complexes display intense absorptions in the visible and ultraviolet regions, which have been analyzed by TDDFT method.

Reaction of pyrrole-2-aldehyde thiosemicarbazone (H 2 L) with [Pd(PPh3)2Cl2] in ethanol afforded the [Pd(PPh3)(HLNS)Cl] and [Pd(PPh3)(LNNS)] complexes, and similar reaction with Na2[PdCl4] afforded the [Pd(HLNS)2] complex.

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Acknowledgements

Financial assistance received from the Department of Science and Technology, West Bengal, India [Grant No. 746(Sanc.)/ST/P/S&T/2G-4/2013] is gratefully acknowledged. Piyali Paul thanks the Council of Scientific and Industrial Research, New Delhi, for her fellowship [Grant No. 09/096(0588)/2009-EMR-I].

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  1. Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata, 700 032, India

    PIYALI PAUL & SAMARESH BHATTACHARYA

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  1. PIYALI PAUL
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  2. SAMARESH BHATTACHARYA
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Correspondence to SAMARESH BHATTACHARYA.

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Supplementary Information

CCDC 989560-989562 contain the supplementary crystallographic data for this paper. Results of TDDFT calculations of [Pd(PPh3)(LNNS)] (table S1) and [Pd(HLNS)2] (table S2), contour plots of selected molecular orbitals of [Pd(PPh3)(LNNS)] (figure S1) and [Pd(HLNS)2] (figure S2) are available as supplementary information.

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PAUL, P., BHATTACHARYA, S. Palladium complexes of pyrrole-2-aldehyde thiosemicarbazone: Synthesis, structure and spectral properties. J Chem Sci 126, 1547–1555 (2014). https://doi.org/10.1007/s12039-014-0699-4

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