Research paperNew trans-[Pd(L-κS,O)2] complexes from N,N-dialkyl-N′-aroylthioureas prepared by photo-induced isomerization of their cis-[Pd(L-κS,O)2] counterparts and their thermal trans-cis isomerization

Add time:09/24/2019    Source:sciencedirect.com

Photo-induced isomerization of cis-[Pd(L1,2-κS,O)2] (HL1 = N,N-diethyl-N′-4-methyl-benzoylthiourea, HL2 = N,N-dimethyl-N′-benzoylthiourea) in acetonitrile solution leads to the reproducible and clean isomerization of rare, new trans-[Pd(L1,2-κS,O)2] complexes, isolated by vapour diffusion crystallization and characterized by single-crystal X-ray diffraction. The isolated trans-[Pd(L1,2-κS,O)2] complexes show higher melting points to the corresponding cis-[Pd(L1,2-κS,O)2] precursors. Time resolved 1H NMR spectroscopy of the isolated trans-[Pd(L1,2-κS,O)2] complexes in chloroform, shows these to spontaneously revert to their cis-[Pd(L1,2-κS,O)2] counterparts in the absence of light by a simple first-order process at relative rates of the order k1 = 0.23 × 10−2 min−1 and k2 = 0.18 × 10−2 min−1 respectively. The reversion trans → cis of these complexes is confirmed also in acetonitrile using reversed-phase HPLC following irradiation of dilute solutions with polychromatic light, at higher relative rates of k1 = 2.6 × 10−2 min−1 and k2 = 4.9 × 10−2 min−1 respectively.

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