Synthesis, characterization, X‐ray structure, electrochemistry, photocatalytic activity and DFT studies of heterotrinuclear Ni(II), Pd(II) and Zn(II) complexes containing a formylferrocene thiosemicarbazone ligand

Abstract

Three complexes of the general formula M{CpFe(η5‐C5H4CH=N–N=C(S)NH2}2 [where M = NiII (2a), PdII (2b) and ZnII (2c)] were synthesized with formylferrocene thiosemicarbazone (1) as a bidentate ligand. All compounds were characterized using conventional spectroscopic and analytical techniques (infrared, 1H and 13C NMR, mass spectrometry and elemental analysis). The molecular structure of 2b was confirmed by single‐crystal X‐ray analysis. To study the photocatalytic activity of the new complexes (2a–c), methylene blue (MB) was selected as a model pollutant. After 180 min, the degradation efficiency of MB reached 87% for 2a, 76% for 2b and 85% for 2c, and all complexes showed a higher photocatalytic activity than the formylferrocene thiosemicarbazone free ligand 1. Theoretical studies were used to characterize the geometry and electronic structure of the compounds and to provide a rational explanation for the measured photocatalytic activity.

Organometallic N‐acylhydrazones of 5‐nitrofuran and 5‐nitrothiophene based: Synthesis, electrochemical, antiparasitic evaluation, and computational study

“…These results agree with those values reported for cyrhetrenyl and cymantrenyl NAHs 13c . The spectra of NF‐1 and NT‐1 compounds displayed the usual pattern for the ferrocenyl unit showing a singlet nearly at δ 4.25 and two resonances between 4.76 and 4.49 ppm 45,46 . In the case of cyrhetrenyl analogs ( 2 ), two signals were observed in the range of 6.27–5.78 ppm, which were associated with the protons of the cyclopentadienyl unit 13c .…”

“…13c The spectra of NF-1 and NT-1 compounds displayed the usual pattern for the ferrocenyl unit showing a singlet nearly at δ 4.25 and two resonances between 4.76 and 4.49 ppm. 45,46 In the case of cyrhetrenyl analogs (2), two signals were observed in the range of 6.27-5.78 ppm, which were associated with the protons of the cyclopentadienyl unit. 13c Two signals between 7.80 and 7.52 ppm were found in the spectra of NF compounds attributed to the furan protons.…”

Transition Metal Complexes of Thiosemicarbazides, Thiocarbohydrazides, and Their Corresponding Carbazones with Cu(I), Cu(II), Co(II), Ni(II), Pd(II), and Ag(I)—A Review

“…The reaction of formylferrocene thiosemicarbazone 118 with Pd(AcO) 2 in an ethanol solution with a 1:2 ratio, and stirring for 24 h gave rise to heterometallic trinuclear complex 119 in 68% yield ( Scheme 57 ) [ 109 ]. Among other complexes (e.g., Ni and Zn), the Pd complex showed higher photocatalytic activity than the formylferrocene thiosemicarbazone free ligand 118 .…”

“…Among other complexes (e.g., Ni and Zn), the Pd complex showed higher photocatalytic activity than the formylferrocene thiosemicarbazone free ligand 118 . Theoretical studies were used to characterize the compounds’ geometry and electronic structure and to provide a rational explanation for the measured [ 109 ]. The molecular structure of 119 displays a square planar geometry with a palladium (II) centre and two bidentate ligands, each of which coordinates to Pd (II) via the imine nitrogen atom and the thioamide sulphur atom of the deprotonated ferrocenyl thiosemicarbazone ligand.…”

“…The molecular structure of 119 displays a square planar geometry with a palladium (II) centre and two bidentate ligands, each of which coordinates to Pd (II) via the imine nitrogen atom and the thioamide sulphur atom of the deprotonated ferrocenyl thiosemicarbazone ligand. Moreover, both ferrocenyl groups in the complex are anti to each other, thus minimizing steric repulsion between them [ 109 ].…”