The First Cyclometallated (1‐Ferrocenylethanone thiosemicarbazone)palladium(II) Compounds − Crystal and Molecular Structure of [Pd{(η⁵‐C₅H₅)Fe(η⁵‐C₅H₃)C(Me)=NN=C(S)NHMe}(PPh₃)]

Abstract

Treatment of the 1‐ferrocenylethanone thiosemicarbazone ligands (η5‐C5H5)Fe(η5‐C5H4)C(Me)=NN(H)C(=S)NHR [R = H (a), Me (b)] with K2[PdCl4] gave the novel heterometallic octanuclear palladium(II) compounds [Pd{(η5‐C5H5)Fe(η5‐C5H3)C(Me)=NN=C(S)NHR}]4 [R = H (1a), Me (1b)] as tetramers, after deprotonation of the NH group, with the ligands acting as terdentate donors through the [C,N,S] atoms. Treatment with nucleophiles cleaves the tetrameric clusters giving compounds in which splitting only of the Pd−Sbridging bonds has occurred. The strength of the Pd−Schelating bond hinders its cleavage. Thus, treatment of 1a or 1b with Ph2P(CH2)nPPh2 [n = 2 (dppe), 3 (dppp), 4 (dppb)] in a 1:2 molar ratio gave the tetranuclear species 2a−4a and 2b−4b, respectively, and treatment with PPh2R gave the dinuclear compounds 5a−7a and 5b−6b [R = Ph (5a, 5b), Et (6a, 6b), Me (7a)]. The complexes described are the first fully characterized cyclometallated palladium(II) complexes with 1‐ferrocenylethanone thiosemicarbazone ligands. The crystal and molecular structure of compound 5b have been determined by X‐ray crystallography. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Cyclometallation of phenylhydrazones: Synthesis, reactivity, crystal structure analysis and novel trinuclear palladium(II) cyclometallated compounds with [C,N,N′] terdentate ligands

“…The upfield shift of the H5 and H11 resonances (as compared to 3a and 1b) was due to shielding by the phosphine phenyl rings [32,33], confirming coordination of the ligand. The 31 P-{ 1 H} NMR spectra showed a singlet resonance at ca.…”

Palladium (II) and platinum (II) complexes containing organometallic thiosemicarbazone ligands: Synthesis, characterization, X-ray structures and antitubercular evaluation

“…Transition metal complexes involving organic-TSCs have emerged as a new alternative to current therapeutic agents [32][33][34][35][36][37][38]. In this regard, we report the synthesis and biological evaluation of cyrhetrenyl and ferrocenyl thiosemicarbazones as potential trypanocidal and antitubercular agents [39].…”

Reaction of (Carbonyl)triruthenium with Acetylferrocene Thiosemicarbazone: Synthesis, X‐ray Diffraction, and Insight into the Solution Structures

“…Because of the ring-current effect, a pronounced tendency towards line broadening was observed for 2 in the nonpolar solvent CDCl 3 . The 1 H NMR spectrum of 2 in [D 6 ]acetone showed that the ring current shields the NH protons and induces large upfield shifts, and as a consequence, the chemical shifts of the two NH protons appear at δ = 2.57 and 2.82 ppm, respectively. There are three peaks corresponding to the substituted Cp ring at δ = 3.76, 4.39, and 4.72 ppm.…”

“…The reaction of Ru 3 (CO) 12 with acetylferrocene thiosemicarbazone in thf at 40°C was also monitored by positiveion ESI-MS analysis. As shown in Figure 4, after heating the reaction system for 30 min, peaks are observed at m/z = 785 and 813, values typical for carbonyl loss from Ru 3 (CO) 9 [L-H] and corresponding to the ions Ru 3 (CO) 6 [L-H] and Ru 3 (CO) 7 [L-H], respectively. A peak corresponding to dinuclear compound Ru 2 (CO) 4 [L] 2 is also observed at m/z = 942.…”

“…Clus-ter 1 has an unsymmetrical triruthenium triangle framework, in which the ligand is deprotonated and acts as a bidentate N,S donor as well as a sulfur bridge. Dinuclear compound 2 consists of a multiring system with a RuS 2 Ru [5] core, and the nondeprotonated ligand is in the unusual cycloruthenated (C ferrocene ,N,S)-tridentate [6] coordination mode, resulting in a significant increase in the stability of 2.…”