Structural and electrochemical studies on trithia macrocyclic complexes of palladium |
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| Institution: | 1. Department of Chemistry, School of Advanced Sciences, VIT University, Vellore, Tamilnadu 632014, India;2. Department of Biosciences, School of Biosciences and Biotechnology, VIT University, Vellore, Tamilnadu 632014, India;3. Department of Chemistry, Amlokchand Mahavidyalaya, Yavatmal, Sant Gadge Baba Amravati University, Amravati 444602, India |
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| Abstract: | The single crystal X-ray structure of Pd(1)2](PF6)2 (1 = 1,4,7-trithiacyclononane) shows a crystallographically centrosymmetric cation with a distorted octahedral stereochemistry about the PdII centre with PdSeq 2.332(3) and 2.311(3) Å for the equatorial thia donors, and PdSax 2.952(4) Å for the two apically coordinated donors. The crystals have space group C2/C, with a 17.879(8), b 15.627(13), c 11.476(8) Å, β 125.92(4)° and Z = 4. Least squares refinement gave R = 0.0565 for 1153 unique observed reflections measured by counter diffracometry using Mo-Kα radiation. This green complex undergoes a chemically reversible, one-electron oxidation in CH3CN, Epa = +0.65V, Epc = +0.56 V vs. Fc/Fc+, ΔEp = 84 mV. Oxidation of Pd(1)2](PF6)2 by controlled potential electrolysis at +0.7 V affords an orange, ESR active product which may be tentatively assigned to the corresponding palladium(III) species. These results are contrasted with data for the related homoleptic thia complexes Pd(L)]2+ (L = 1,4,8,11-tetrathiacyclotetradecane (2), 1,4,7,10,13,16-hexathiacyclooctadecane (3)). The syntheses of the complexes cis-Pd(1)Cl2], cis-Pt(1)Cl2], cis-Pd(1)(PPh3)2](PF6)2 and cis-Pt(1)(PPh3)2](PF6)2 are also described. |
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