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Probing the Structure of the 1:1 Hydrogen-Bonded Complexes of Metallocenes with HCl.
J Phys Chem A
February 2024
Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45219, United States.
Matrix isolation infrared spectroscopy combined with density functional calculations has been used to form, isolate, and characterize the 1:1 hydrogen-bonded complexes of HCl with ferrocene and ruthenocene. Two unique structures were calculated for each complex, analogous to the two binding sites proposed for the attachment of proton to these metallocenes. The spectra, combined with calculated shifts of the H-Cl stretching mode, support the formation of a complex with the HCl hydrogen bonding to one of the cyclopentadienyl rings, exo to the plane of the ring.
View Article and Find Full Text PDFMultidisciplinary Preclinical Investigations on Three Oxamniquine Analogues as New Drug Candidates for Schistosomiasis*.
Chemistry
November 2020
Chimie ParisTech, PSL University, CNRS, Institute of Chemistry for Life and Health Sciences, Laboratory of Inorganic Chemical Biology, 75005, Paris, France.
Schistosomiasis is a disease of poverty affecting millions of people. Praziquantel (PZQ), with its strengths and weaknesses, is the only treatment available. We previously reported findings on three lead compounds derived from oxamniquine (OXA), an old antischistosomal drug: ferrocene-containing (Fc-CH -OXA), ruthenocene-containing (Rc-CH -OXA) and benzene-containing (Ph-CH -OXA) OXA derivatives.
View Article and Find Full Text PDFSteric and Electronic Effect of Cp-Substituents on the Structure of the Ruthenocene Based Pincer Palladium Borohydrides.
Molecules
May 2020
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilova Str., Moscow 119991, Russia.
Ruthenocene-based PCP pincer ligands were used to synthesize novel pincer palladium chloride Rc[PCP]PdCl () and two novel palladium tetrahydroborates Rc[PCP]Pd(BH) () and Rc[PCP]Pd(BH) (), where Rc[PCP] = κ-{2,5-(tBuPCH)CH}Ru(Cp) (Cp = CMeCF), and Rc*[PCP] = κ-{2,5-(tBuPCH)CH}Ru(Cp*) (Cp* = CMe). These coordination compounds were characterized by X-ray, NMR and FTIR techniques. Analysis of the X-ray data shows that an increase of the steric bulk of non-metalated cyclopentadienyl ring in and relative to non-substituted Rc[PCP]Pd(BH) analogue (; where Rc[PCP] = κ-{2,5-(tBuPCH)CH}Ru(Cp), Cp = CH) pushes palladium atom from the middle plane of the metalated Cp ring in the direction opposite to the ruthenium atom.
View Article and Find Full Text PDFOrganometallic nucleoside analogues: effect of the metallocene metal atom on cancer cell line toxicity.
Dalton Trans
January 2020
School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK.
A new chiral organometallic nucleoside analogue containing ruthenocene is reported, in which alkylthymine and alkylhydroxyl groups are attached in adjacent positions on one cyclopentadienyl ring. The synthetic procedures for this metallocene derivative and two control compounds are described, along with their characterisation by cyclic voltammetry and X-ray crystallography. Their biological activities in a human pancreatic cancer cell line (MIA-Pa-Ca-2) were significantly lower than those of three previously reported analogous ferrocene compounds, indicating that the choice of metallocene metal atom (Fe or Ru) plays a pivotal role in determining the anticancer properties of these nucleoside analogues, which in turn suggests a different mode of action from that of a conventional nucleoside analogue.
View Article and Find Full Text PDFMixed-Valent Ruthenocene-Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites.
Inorg Chem
February 2019
University of Konstanz , Department of Chemistry , Universitätsstraße 10, 78457 Konstanz , Germany.
Ruthenocene-vinylruthenium conjugates Rc/Rc*-CH═CH-Ru(CO)(L)(P Pr) (Rc = (η-CH)Ru(η-CH); Rc* = (η-CMe)Ru(η-CH); L = Cl or κ O, O' -acetylacetonato) have been prepared and investigated in their neutral, mono-, and dioxidized states by cyclic voltammetry, IR and UV/vis/NIR spectroelectrochemistry, and EPR spectroscopy. Their corresponding radical cations are (almost) completely delocalized mixed-valent systems as indicated by the low half-widths, the absence of solvatochromism, and the low-energy cutoff of their IVCT bands in the near-infrared (NIR) and their IR and EPR spectroscopic signatures. The degree of electronic coupling even exceeds that of their ferrocene analogs despite comparable differences between the intrinsic half-wave potentials of the vinylruthenium and the metallocenyl entities and substantially smaller half-wave potential splittings, Δ E, in the ruthenocene congeners.
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