Copper(II) and nickel(II) complexes of 2,3-butanedione bis(N(3)-substituted thiosemicarbazones)

West, Douglas X.; Ives, Janeice S.; Bain, Gordon A.; Liberta, Anthony E.; Valdés-Martı́nez, Jesús; Ebert, K. H.; Hernández‐Ortega, Simón

doi:10.1016/s0277-5387(96)00468-8

Cited by 97 publications

(59 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The position of the NH 2 and NH bands showed that the former group was not coordinated. The displacement of the ν(CϭN) band towards lower wavenumbers upon complex formation [21] is in contrast with other thiosemicarbazone complexes in which the shift is towards higher wavenumbers, probably due to the presence of the five-membered metallacycle in compounds 1a and 1b. [22] No ν(PdϪCl) band was found in the IR spectra of the compounds, indicating the absence of a chloride ligand in the coordination sphere of the metal center.…”

contrasting

confidence: 60%

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)]

et al. 2004

View full text Add to dashboard Cite

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)

show abstract

contrasting

confidence: 60%

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)]

et al. 2004

View full text Add to dashboard Cite

show abstract

“…[1] West et al have discussed the crystal structures of a number of bis(thiosemicarbazones), derived from butanedione, and their metal complexes. [25] The thiosemicarbazides, which were not commercially available, were made according to the Scovill procedure. [19] We have also prepared a number of bis(thiosemicarbazones) and their copper(II) complexes by this method.…”

Section: Route C-formation Of the C=n (1) Bondmentioning

confidence: 99%

Ligands for Molecular Imaging: The Synthesis of Bis(thiosemicarbazone) Ligands

Christlieb

Dilworth

2006

Chemistry A European J

View full text Add to dashboard Cite

Bis(thiosemicarbazones) have been of interest to chemists for over fifty years; they display antitumour, antibiotic and antiviral properties. Recently it has become apparent that they may also provide a convenient way of labelling biologically active molecules by using metallic radionuclides and/or fluorescence. Although apparently simple, the synthesis of bis(thiosemicarbazone) ligands can be problematic. This article provides a summary of the published literature, based on the synthetic strategies used and indicates some of the difficulties that may arise.

show abstract

“…[60,70] Copper(II)-bis(thiosemicarbazonato) complexes typically exhibit copper hyperfine splitting of around 91.0 G, with nitrogen superhyperfine coupling constants around 16.0 G and line intensities in a ratio of 1:2:3:2:1. The values derived for 1, are slightly lower than those found by West et al [70] and the low g iso value of 2.055, is indicative of the covalent nature of the metal-ligand bonding in these copper(II) complexes. [71] RT solution-phase spectra were simulated with EasySpin by using the fast-motion regime.…”

mentioning

confidence: 99%

Spectroelectrochemical and Computational Studies on the Mechanism of Hypoxia Selectivity of Copper Radiopharmaceuticals

Holland

Barnard

Collison

et al. 2008

Chemistry A European J

128

View full text Add to dashboard Cite

Detailed chemical, spectroelectrochemical and computational studies have been used to investigate the mechanism of hypoxia selectivity of a range of copper radiopharmaceuticals. A revised mechanism involving a delicate balance between cellular uptake, intracellular reduction, reoxidation, protonation and ligand dissociation is proposed. This mechanism accounts for observed differences in the reported cellular uptake and washout of related copper bis(thiosemicarbazonato) complexes. Three copper and zinc complexes have been characterised by X-ray crystallography and the redox chemistry of a series of copper complexes has been investigated by using electronic absorption and EPR spectroelectrochemistry. Time-dependent density functional theory (TD-DFT) calculations have also been used to probe the electronic structures of intermediate species and assign the electronic absorption spectra. DFT calculations also show that one-electron oxidation is ligand-based, leading to the formation of cationic triplet species. In the absence of protons, metal-centred one-electron reduction gives the reduced anionic copper(I) species, [CuIATSM](-), and for the first time it is shown that molecular oxygen can reoxidise this anion to give the neutral, lipophilic parent complexes, which can wash out of cells. The electrochemistry is pH dependent and in the presence of stronger acids both chemical and electrochemical reduction leads to quantitative and rapid dissociation of copper(I) ions from the mono- or diprotonated complexes, [CuIATSMH] and [Cu(I)ATSMH2]+. In addition, a range of protonated intermediate species have been identified at lower acid concentrations. The one-electron reduction potential, rate of reoxidation of the copper(I) anionic species and ease of protonation are dependent on the structure of the ligand, which also governs their observed behaviour in vivo.

show abstract

Copper(II) and nickel(II) complexes of 2,3-butanedione bis(N(3)-substituted thiosemicarbazones)

Cited by 97 publications

References 18 publications

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)]

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)]

Ligands for Molecular Imaging: The Synthesis of Bis(thiosemicarbazone) Ligands

Spectroelectrochemical and Computational Studies on the Mechanism of Hypoxia Selectivity of Copper Radiopharmaceuticals

Contact Info

Product

Resources

About

Copper(II) and nickel(II) complexes of 2,3-butanedione bis(N(3)-substituted thiosemicarbazones)

Cited by 97 publications

References 18 publications

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)]

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)]

Ligands for Molecular Imaging: The Synthesis of Bis(thiosemicarbazone) Ligands

Spectroelectrochemical and Computational Studies on the Mechanism of Hypoxia Selectivity of Copper Radiopharmaceuticals

Contact Info

Product

Resources

About

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)]

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)]