Wydział Chemii

Hanna Pruchnik

Tadeusz Lis

Małgorzata Latocha

Aleksandra Zielińska

Florian P. Pruchnik

2016

Journal of Inorganic Biochemistry

156

14-21

10.1016/j.jinorgbio.2015.12.001

Naukowa

Angielski

Artykuł

Water soluble and air stable P(RCOOH)₃(R=C₂H₄) (TCEP) is an efficient reducing agent used in biochemistry to break S-S bond in peptides, proteins and other compounds containing S-S bonds. The similarity between the coordination chemistry of Pd(II) and Pt(II) led to the investigations of antitumor activity of palladium(II) compounds however the Pd(II) complexes with TCEP were not investigated. New palladium(II) complexes with (TCEP):trans-[PdCl₂(TCEP)₂] (1) andtrans-[Pd₂(μ-Cl)₂Cl₂(TCEP)₂] (2) were fully characterized by¹H,¹³C,³¹P NMR, IR and ESI-MS spectroscopic techniques. Complexes are stable in non-aqueous DMSO and DMF. In aqueous solutions Cl ligands are substituted by COO groups of phosphines. Complex2, after crystallization from water gives polymeric compound with bridging phosphine ligand [PdCl{P(RCOO-κO-μ-O′)(RCOOH)₂-κP}] (3). Structures oftrans-[PdCl₂{P(RCOOD)₃}₂] (1a),trans-[Pd₂(μ-Cl)₂PdCl₂{P(RCOOD)₃}₂] (2a), and [PdCl{P(RCOO-κO-μ-O′)(RCOOD)₂-κP}]_n(3a) have been determined by X-ray crystallography. NMR and ESI-MS spectra reveal that [PdP₂(RCOO-κO)₂(RCOO)_n(RCOOH)_4−n]^n-complexes are formed in aqueous solution of1. Geometry optimization in the gas phase at the B3LYP/3-21G** level indicated that complex2with butterfly structure is more stable than that with coplanar coordination. In aqueous solution of2, the main products [Pd₂{P(RCOO-κO-μ-O′)(RCOO-κO)(RCOOH)}₂] and [Pd{P(RCOO-κO)₂(RCOOH)}(H₂O)] exist in equilibrium which depends on temperature: content of mononuclear compound increases as the temperature is raised. Complexes1and2are active agents against melanoma and breast cancer cells.

palladium, Phosphine, Antitumor, density functional calculations

http://dx.doi.org/10.1016/j.jinorgbio.2015.12.001

http://www.elsevier.com