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Construction of alkyl-substituted pentaphosphido ligands in the coordination sphere of cobalt.

ABSTRACT: Rare mono- and diorganopentaphosphido cobalt complexes are accessible by P-P condensation using the unprecedented, reactive cobalt-gallium tetraphosphido complex [K(dme)₂{(^MesBIAN)Co(μ-η⁴:η²-P₄)Ga(nacnac)}] (2). Compound 2 was prepared in good yield by reaction of [K(Et₂O){(^MesBIAN)Co(η⁴-1,5-cod)}] [1, BIAN = bis(mesitylimino)acenaphthene diimine, cod = 1,5-cyclooctadiene] with [Ga(nacnac)(η²-P₄)] (nacnac = CH[CMeN(2,6-iPr₂C₆H₃)]₂). Reactions with R₂PCl (R = iPr, tBu, and Cy) selectively afford [(^MesBIAN)Co(cyclo-P₅R₂)] (3a-c), which feature η⁴-coordinated 1,1-diorganopentaphosphido ligands. The mechanism of formation of these species has been studied by ³¹P{¹H} NMR spectroscopy and DFT calculations. In the case of 3a (R = iPr), it was possible to identify the intermediate [(^MesBIAN)Co(μ-η⁴:η²-P₅iPr₂)Ga(nacnac)] (4) by single-crystal X-ray diffraction. A related, monosubstituted organopentaphosphido cobalt complex [(^MesBIAN)Co(μ-η⁴:η¹-P₅ tBu)GaCl(nacnac)] (5) was isolated by reacting dichloroalkylphosphane tBuPCl₂ with 2. Heterobimetallic complexes such as 2 thus may enable the targeted construction of a range of new metal-coordinated polyphosphorus frameworks by P-P condensation.

SUBMITTER: Ziegler CGP

PROVIDER: S-EPMC6357856 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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Construction of alkyl-substituted pentaphosphido ligands in the coordination sphere of cobalt.

Ziegler Christoph G P CGP Maier Thomas M TM Pelties Stefan S Taube Clemens C Hennersdorf Felix F Ehlers Andreas W AW Weigand Jan J JJ Wolf Robert R

Chemical science 20181204 5

Rare mono- and diorganopentaphosphido cobalt complexes are accessible by P-P condensation using the unprecedented, reactive cobalt-gallium tetraphosphido complex [K(dme)2{(MesBIAN)Co(μ-η4:η2-P4)Ga(nacnac)}] (2). Compound 2 was prepared in good yield by reaction of [K(Et2O){(MesBIAN)Co(η4-1,5-cod)}] [1, BIAN = bis(mesitylimino)acenaphthene diimine, cod = 1,5-cyclooctadiene] with [Ga(nacnac ...[more]

PMID: 30809344

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Project description:Finding new sources of biologically active compounds for anticancer or antimicrobial therapies remains an active area of research. Azothioformamides (ATFs) with a 1,3 N=N-C=S heterodiene backbone are a new class of biologically active compounds that chelate metals (e.g., Cu) forming stable ATF metal coordination complexes. In this study, ATF ligands were prepared with pyrrolidine, piperidine, N-methylpiperazine, and morpholine substituents on the formamide as to add more heterocyclic drug-like character for biological studies. Formamide derivatives were then complexed with various Cu(I) salts to form coordination complexes. Cu(I) salts were selected as to create potential bioactive compounds with less toxicity. Binding association constants of each Cu(I) salt to ATF ligands were extrapolated from UV-vis titration studies and were corroborated with DFT calculations using a hybrid functional B3LYP method. It was observed that the smaller pyrrolidine functionalized ATFs bound to the Cu(I) salts had stronger binding than any of the larger six-membered-ring heterocycles with association values in the 104 - 105 M-1 range. The ATF-Cu(I) salt coordination complexes were then evaluated for antimicrobial activity against two bacteria (Staphylococcus aureus, Escherichia coli), one yeast (Candida albicans), four human cancer lines (A-549, K-562, HT-1080, MDA-MB-231), and two normal human lines (MRC-5, HFF). The ATF ligands themselves were inactive against all microbes and most human lines except K-562 cells, which were sensitive to three of the four ligands (IC50's = 7.0-25.5 μM). Most ATF-Cu(I) complexes showed low to medium micromolar activity against Candida albicans (IC50's 2.6-24.8 μM) and Staphylococcus aureus (IC50's = 3.4-37.7 μM), with increasing activity corresponding to complexes with higher binding association constants. The antiproliferative properties of ATF-Cu(I) metal salt complexes against mammalian cells were mixed, with low to medium micromolar activity across all cell lines. Notably, several ATF-Cu(I) salt coordination complexes showed submicromolar activity against the HT-1080 fibrosarcoma line (0.52-0.69 μM). The results demonstrate promising activity of ATF-Cu(I) complexes, particularly with pyrrolidine as the formamide component. These studies suggest that the stronger binding association values correlate to higher levels of biological activity.

Dataset Information

Construction of alkyl-substituted pentaphosphido ligands in the coordination sphere of cobalt.

Publications

Construction of alkyl-substituted pentaphosphido ligands in the coordination sphere of cobalt.

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