Ruthenium(II) mediated C–H activation of substituted acetophenone thiosemicarbazones: Synthesis, structural characterization, luminescence and electrochemical properties

Cyclometallated ruthenium(II) carbonyl complexes with 1-pyrenaldehyde 4-R-3-thiosemicarbazones: Regioselective ruthenation of the 1-pyrenyl group

“…Absence of these bands indicates coordination of the thioamidate-S to the ruthenium(II) centre in the complexes. 28,[47][48][49][50] The complexes display the ν C=N stretch in the region 1555-1585 cm −1 which is at a lower frequency than that of the free H 2 L n (∼1600 cm −1 ) indicating coordination of the azomethine nitrogen to the metal centre. 28,[48][49][50] The typical strong band for the terminally coordinated carbonyl group in 1−6 is observed in the range 1918-1956 cm −1 .…”

“…28,[47][48][49][50] The complexes display the ν C=N stretch in the region 1555-1585 cm −1 which is at a lower frequency than that of the free H 2 L n (∼1600 cm −1 ) indicating coordination of the azomethine nitrogen to the metal centre. 28,[48][49][50] The typical strong band for the terminally coordinated carbonyl group in 1−6 is observed in the range 1918-1956 cm −1 . 29,32,48,50 Three strong bands displayed by all the complexes at ∼520, ∼695 and ∼745 cm −1 are attributed to the metal coordinated EPh 3 ligands.…”

“…Interestingly, analogous monocyclic aromatic aldehyde thiosemicarbazones are known to provide ortho-ruthenated complexes having 5,5-membered fused chelate rings, where the ligands act as CNS-donor. [28][29][30][31][32] It may be noted that among various Schiff bases containing nitrogen and sulphur donor atoms, thiosemicarbazones are quite unique with respect to their selectivity, sensitivity and the ability to adopt a variety of coordination modes towards various metal ions. 32,33 In view of the above facts, we have invesigated the ruthenium(II) coordination chemistry with 1-pyrenaldehyde 4-R-3-thiosemicarbazones (H 2 L n , where the two H's represent the dissociable thioamide and pyrenyl protons) (scheme 1).…”

Stabilization of CuII–I Bonds Using 2‐Benzoylpyridine Thiosemicarbazones – Synthesis, Structure, Spectroscopy, Fluo­rescence, and Cyclic Voltammetry

“…The oxidative and reductive responses of thiosemicarbazones coordinated to Ru, Rh, Pd, and Ir have also been reported. [37][38][39][40] …”

“…[42] For example, copper(II) halides (Cl/Br) with neutral thiosemicarbazones involved the deprotonation of the -N 2 H moiety to form copper(II) complexes (Scheme 4), as represented in Equation (1). The resulting complexes have anionic thiosemicarbazone ligands and are either four-coordinate square-planar {Cu II X(NNS)} complexes (Scheme 4, structure IV), [24,26,36,38,[42][43][44][45][46][47] or five-coordinate square-pyramidal complexes with bridging halogen or sulfur atoms and {Cu II X(μ-S) 2 NN} (Scheme 4, structure V) [24] and {Cu II (μ-X) 2 NNS} (Scheme 4, structure VI; X = Cl or Br in IV-VI) coordination cores. [45] On the other hand, the reactions of thiosemicarbazones with copper(I) …”