ZEJQIS: bis(N-[2,2-dimethyl-1-(oxo)propyl]-2-methylpyrrolidine-1-carboximidothioato)-platinum(ii)

This item contains metadata for an Experimental Crystal Structure Determination and is published at https://www.ccdc.cam.ac.uk/structures/search?id=doi:10.5517/ccdc.csd.cc2c29tl&amp;sid=DataCite. The data are linked to the published article: H.A. Nkabyo, A.B. Oyenihi, C.M. Joseph, O.O. Olaoye, A.S. Lopis, R.C. Luckay. 2022. Platinum(II) complexes bearing asymmetrically substituted pivaloylthioureas: Synthesis, crystal structures, DFT and antioxidant studies. In: Polyhedron, Volume 226, https://doi.org/10.1016/j.poly.2022.116076.Three new platinum(II) complexes derived from asymmetrically di-substituted pivaloylthiourea ligands (L^1–3) are synthesized and characterized by ¹H, and ¹⁹⁵Pt{¹H} NMR. The ligands and PtL^1–3 complexes display configurational <i>E,Z</i> isomerism evinced by distinct sets of ¹H, ¹⁹⁵Pt{¹H} NMR resonances observed in <i>d</i>ichloromethane‑<i>d</i>_<em>2</em>. Single-crystal X-ray diffraction studies reveal a bidentate <i>cis</i>-PtL^1–3 coordination mode, in which two sulfur and oxygen donor atoms bind to Pt(II) forming a six-membered chelate. In addition, the <i>EE</i> isomers were preferentially isolated in acetonitrile for <i>cis</i>-PtL¹ and <i>cis</i>-PtL², while <i>ZZ</i> was obtained for <i>cis</i>-PtL³ with <i>N</i>-phenyl substituent. The relative energies of the <i>cis</i>-<i>ZZ</i>-Pt-L^1–3, <i>cis</i>-<i>EZ</i>-Pt-L^1–3, <i>cis</i>-<i>EE</i>-Pt-L^1–3 configurational isomers are obtained by DFT analysis at the M06-2X/def2-SVP level of theory using an implicit acetonitrile solvent. Moreover, the structural studies indicate a potential intra-electron transfer from d_z² (HOMO) to d_x²_-y² (LUMO), with a reduced electron affinity at the LUMO level for the <i>cis</i>-<i>ZZ/ZE/EE</i>-Pt-L^1–3 structures. The antioxidant capacity of the L^1–3 ligands and <i>cis</i>-PtL^1–3 were evaluated using the ORAC, DPPH radical scavenging and FRAP methods. The free L^1–3 ligands showed higher antioxidant activities in comparison to their coordinated <i>cis</i>-PtL^1–3 complexes.<br><br>