38 research outputs found
Coordination of di- and triimine ligands at ruthenium(II) and ruthenium(III) centers: structural, electrochemical and radical scavenging studies
Herein, we explore the coordination of di- and triimine chelators at
ruthenium(II) and ruthenium(III) centers. The reactions of 2,6-bis-((4-
tetrahydropyranimino)methyl)pyridine (thppy), N1,N2-bis((3-chromone)
methylene)benzene-1,2-diamine (chb), and tris-((1H-pyrrol-2-ylmethylene)
ethane)amine (H3pym) with trans-[RuIICl2(PPh3)3] afforded the diamagnetic
ruthenium(II) complex cis-[RuCl2(thppy)(PPh3)] (1) and the paramagnetic
complexes [mer-Ru2(μ-chb)Cl6(PPh3)2] (2), and [Ru(pym)] (3), respectively.
The complexes were characterized by IR, NMR, and UV–vis spectroscopy
and molar conductivity measurements. The structures were confirmed by
single crystal X-ray diffraction studies. The redox properties of the metal
complexes were probed via cyclic- and squarewave voltammetry. Finally, the
radical scavenging capabilities of the metal complexes towards the NO and
2,2-di(4-tert-octylphenyl)-1-picrylhydrazyl (DPPH) radicals were investigate
Ruthenium complexes with Schiff base ligands containing benz(othiazole/imidazole) moieties: Structural, electron spin resonance and electrochemistry studies
Novel ruthenium(II/III) complexes of Schiff bases containing benzimidazole (bz) or benzothiazole (bs)
moieties were isolated: the diamagnetic ruthenium complex, cis-[RuIICl2(bzpy)(PPh3)2] (1) was formed
from the 1:1 M reaction between N-((pyridine-2-yl)methylene)-1H-benzimidazole (bzpy) and metal precursor,
trans-[RuCl2(PPh3)3]. The same metal precursor, when reacted with the benzimidazole-derived
Schiff bases [N-(2-hydroxybenzylidene)-benzothiazole (Hbsp) and N-(2-hydroxybenzylidene)-benzimidazole
(Hbzp)], afforded the paramagnetic ruthenium(III) complexes [RuCl(bsp)2(PPh3)] (2) and
trans-[RuCl(bzp)(PPh3)2] (3), respectively. These metal complexes were characterized via IR, mass and
UV–Vis spectroscopy, elemental analysis, single crystal XRD analysis as well as conductivity measurements.
Their redox properties were probed by voltammetry and accompanying UV–Vis spectroelectrochemistry
experiments. Structural features of complex 1 were further investigated by multinuclear (1H
and 31P) NMR spectroscopy
4′-[2-(TrifluoroÂmethÂyl)phenÂyl]-2,2′:6′,2′′-terpyridine
The title compound, C22H14F3N3, is a versatile tridentate N-donor ligand consisting of a terpyridyl (terpy) molecule substituted in the 4′-position by a phenyl group, itself substituted in an ortho-position by a bulky trifluoroÂmethyl group. The phenyl ring is twisted as a result of steric interÂactions involving the bulky trifluoroÂmethyl substituent. This is reflected in the dihedral angle between the mean plane through the C atoms of the phenyl ring and the terpyridyl unit being 69.2 (1)°. The crystal structure contains no short van der Waals contacts. However, the terpy units stack in a head-to-tail orientation perpendicular to the c axis. The structure is is loosely stabilized by π–π interÂactions between the terminal pyridine rings of adjacent molÂecules along the stack. The perpendicular distance between the mean planes through the terpy moieties of adjacent molÂecules is 3.4 (1) Å
Redox behaviour of cymantrene Fischer carbene complexes in designing organometallic multi-tags
Please read abstract in the article.This work is supported by the National Research Foundation (NRF) of South Africa, (D.I.B., Grant number 76226;J.C.S., Grant number 81829). I. F. acknowledges the Spanish MICINN and CAM (Grants CTQ2010-20714-CO2-01/BQU, Consolider-Ingenio 2010, CSD2007-00006, S2009/PPQ-1634). O.Q.M. acknowledges financial support
from the University of KwaZulu-Natal and the NRF.http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-37652015-04-30hb201
A cytotoxic bis(1,2,3-triazol-5-ylidene)carbazolide gold(III) complex targets DNA by partial intercalation
The syntheses of bis(triazolium)carbazole precursors
and their corresponding coinage metal (Au, Ag) complexes
are reported. For alkylated triazolium salts, di- or tetranuclear
complexes with bridging ligands were isolated, while the bis
(aryl) analogue afforded a bis(carbene) AuI
-CNC pincer
complex suitable for oxidation to the redox-stable [AuIII(CNC)
Cl]+ cation. Although the ligand salt and the [AuIII(CNC)Cl]+
complex were both notably cytotoxic toward the breast
cancer cell line MDA-MB-231, the AuIII complex was somewhat
more selective. Electrophoresis, viscometry, UV-vis, CD and LD
spectroscopy suggest the cytotoxic [AuIII(CNC)Cl]+ complex
behaves as a partial DNA intercalator. In silico screening
indicated that the [AuIII(CNC)Cl]+ complex can target DNA
three-way junctions with good specificity, several other
regular B-DNA forms, and Z-DNA. Multiple hydrophobic πtype interactions involving T and A bases appear to be
important for B-form DNA binding, while phosphate O···Au
interactions evidently underpin Z-DNA binding. The CNC
ligand effectively stabilizes the AuIII ion, preventing reduction
in the presence of glutathione. Both the redox stability and
DNA affinity of the hit compound might be key factors
underpinning its cytotoxicity in vitro.https://chemistry-europe.onlinelibrary.wiley.com/journal/15213765pm2021ChemistryPhysiolog
Complexities of the interaction of Ni(II), Pd(II) and Pt(II) pyrrole-imine chelates with human serum albumin
Human serum albumin (HSA) efficiently transports drugs in vivo: most are organic. Here, HSA binding affinity and site specificity are shown to depend on the identity of the d8 metal ion in Ni(II), Pd(II) and Pt(II) chelates of the bis(pyrrole-imine) ligand H2PrPyrr. Fluorescence quenching data for native and probe-bound HSA showed sites close to Trp-214 (subdomain IIA) are targeted. The Stern-Volmer constants, KSV, ranged from 10^4 M^(-1) to 10^5 M^(-1) while the affinity constants, Ka, ranged from 3.5 x 10^3 M^(-1) to 1 x 10^6 M^(-1) at 37 degrees Centigrade, following the order Pd(PrPyrr) > Pt(PrPyrr) > Ni(PrPyrr) > H2PrPyrr. Ligand uptake is enthalpically driven, hinging mainly on London dispersion forces. Induced CD spectra for the protein-bound ligands could be simulated by hybrid QM:MM TD-DFT methods, proving that the metal chelates neither decompose nor demetallate after uptake by HSA. Transport and delivery of the metal chelates by HSA in vivo could therefore be feasible