Dataset Information

Cobaltocenylidene: A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex.

ABSTRACT: Oxidative addition of cobaltoceniumdiazonium bis(hexafluoridophosphate) with (pseudo)halide aurates gave gold(III) complexes containing zwitterionic cobaltoceniumide as a ligand. Its selenium derivative, cobaltoceniumselenolate, was obtained by an electrophilic aromatic substitution reaction of iodocobaltocenium iodide with Na2 Se. Spectroscopic and structural data in combination with DFT calculations showed that this cobaltocenylidene species is a mesoionic carbene quite different from common N-heterocyclic carbenes. Its ligand properties (TEP, singlet-triplet gap, nucleophilicity, ?-acidity, Brønsted basicity) are in part comparable to those of cyclic (amino)(alkyl/aryl)carbenes. Electrochemistry data showed that the mesoionic cobaltoceniumides are more electron-rich than their parent ferrocenes. The reversible reduction of the tricyanido gold complex appears 50?mV negative of the cobaltocenium/cobaltocene couple, whereas that of the selenide derivative is shifted cathodically by 550?mV.

SUBMITTER: Vanicek S

PROVIDER: S-EPMC5888181 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature

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Cobaltocenylidene: A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex.

Vanicek Stefan S Podewitz Maren M Hassenrück Christopher C Pittracher Michael M Kopacka Holger H Wurst Klaus K Müller Thomas T Liedl Klaus R KR Winter Rainer F RF Bildstein Benno B

Chemistry (Weinheim an der Bergstrasse, Germany) 20180205 13

Oxidative addition of cobaltoceniumdiazonium bis(hexafluoridophosphate) with (pseudo)halide aurates gave gold(III) complexes containing zwitterionic cobaltoceniumide as a ligand. Its selenium derivative, cobaltoceniumselenolate, was obtained by an electrophilic aromatic substitution reaction of iodocobaltocenium iodide with Na<sub>2</sub> Se. Spectroscopic and structural data in combination with DFT calculations showed that this cobaltocenylidene species is a mesoionic carbene quite different fr ...[more]

PMID: 29328533

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Project description:BACKGROUND: Cancer treatment using gold (I) complexes is becoming popular. In this study, a gold (I) N-heterocyclic complex designated as complex 3 was synthesized, its cytotoxicity was examined, and its anti-melanoma activity was evaluated in vitro and in vivo. METHODS: Viability of cancer cells was determined by MTT assay upon treatment with various concentrations of a gold (I) N-heterocyclic carbene complex (complex 3) in a dose and time dependent manner. Mouse melanoma cells B16F10 were selected for further apoptotic studies, including flowcytometric analysis of annexin binding, cell cycle arrest, intracellular ROS generation and loss in the mitochondrial membrane potential. ELISA based assays were done for caspase activities and western blots for determining the expression of various survival and apoptotic proteins. Immunocytology was performed to visualize the translocation of p53 to the nucleus. B16F10 cells were inoculated into mice and post tumor formation, complex 3 was administered. Immunohistology was performed to determine the expressions of p53, p21, NF-?B (p65 and p50), MMP-9 and VEGF. Student's t test was used for determining statistical significance. The survival rate data were analyzed by Kaplan-Meier plots. RESULTS: Complex 3 markedly inhibited the growth of HCT 116, HepG2, and A549, and induced apoptosis in B16F10 cells with nuclear condensation, DNA fragmentation, externalization of phosphatidylserine, activation of caspase 3 and caspase 9, PARP cleavage, downregulation of Bcl-2, upregulation of Bax, cytosolic cytochrome c elevation, ROS generation, and mitochondrial membrane potential loss indicating the involvement of an intrinsic mitochondrial death pathway. Further, upregulation of p53, p-p53 (ser 15) and p21 indicated the role of p53 in complex 3 mediated apoptosis. The complex reduced tumor size, and caused upregulation of p53 and p21 along with downregulation of NF-?B (p65 and p50), VEGF and MMP-9. These results suggest that it induced anti-melanoma effect in vitro and in vivo by modulating p53 and other apoptotic factors. CONCLUSIONS: The gold (I) N-heterocyclic carbene complex (C22H26N6AuO2PF6) designated as complex 3 induced ROS and p53 dependent apoptosis in B16F10 cells involving the mitochondrial death pathway along with suppression of melanoma tumor growth by regulating the levels of pro and anti apoptotic factors (p53, p21, NF-?B, VEGF and MMP-9).

Dataset Information

Cobaltocenylidene: A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex.

Publications

Cobaltocenylidene: A Mesoionic Metalloceno Carbene, Stabilized in a Gold(III) Complex.

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