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• 1663-45-2 1,2-bis-(diphenylphosphino)ethane 

Relevant academic research and scientific papers

Facile synthesis of heterobimetallic [FeII(μ-diphosphine)RuII] and homobimetallic [FeII(μ-diphosphine)FeII] complexes and their in vitro cytotoxic activity on cisplatin-resistant cancer cells

A series of heterobimetallic [Fe,Ru] and homobimetallic [Fe,Fe] complexes, featuring μ -diphosphine bridges between the two metal centres, are reported along with their in vitro cytotoxicity activity on the A2780cisR cell-line. The known starting material [CpFe(CO)2(CH3)] (Cp = η5-C5H5) (1) was reacted with dppe (1,2-bis(diphenylphosphino)ethane) forming the known mononuclear κ1-dppe complex: [CpFe(CO)(COCH3)(κ1-dppe)] (2) and the known dinuclear complex: and [[CpFe(CO)(COCH3)]2(μ-dppe)] (3). Dimer cleavage reactions between complex 2 and two ruthenium arene complexes [(η6-p-cymene)RuCl2]2 and [(η6-benzene)RuCl2]2 formed two new heterobimetallic complexes: [CpFe(CO)(COCH3)(μ-dppe)Ru(η6-cymene)Cl2] (4) and [CpFe(CO)(COCH3)(μ-dppe)Ru(η6-C6H6)Cl2] (5). A homobimetallic system, [[CpFe(CO)(I)]2(μ-dppb)] (6) was obtained by the facile reaction between of [CpFe(CO)2I] and 1,4-bis(diphenylphosphino)butane (dppb). Complex 6 was methylated using MeLi to generate the more lipophilic complex [[CpFe(CO)(CH3)]2(μ-dppb)] (7). All of the complexes were fully characterized by spectroscopy (1H, 13C {1H}, 31P {1H} NMR; FTIR, UV–Vis), and high resolution mass spectrometry (HRMS). Density functional theory calculations (DFT) (Level of theory B3LYP, basis set for H, C, P, O, Cl is 6-31+G(d,p) and for Ru, Fe, I is DGDZVP) on complexes 5 and 6 are also reported. An excellent agreement between the DFT calculated infra-red (IR) spectra of the optimised geometries of 5 and 6 was found with the experimentally determined spectra. In vitro cytotoxicity studies of all complexes was carried out on A2780cisR (cisplatin resistant ovarian cancer cell-line) and compared to cisplatin as a positive control and RAPTA-C as a negative control. Although limited to only one cell-line, the results show that the heterobimetallic complexes 4 and 5 are the most cytotoxic (IC50 = 4.9 ± 0.4 μM and 6.5 ± 0.1 μM respectively), whilst the dinculear [Fe,Fe] complexes exhibit no, or very low cytotoxicity.

Synthesis and x-ray structure of [(η5-C5H5)Fe(CO)C(O)Me](μ-η 1:η1-dppe)[(η4-exo-MeC 5H5)Fe(CO)2]

The 1:1 mixture of (η5-C5H5)Fe(CO)2I and (η5-C5H5)Fe(CO)C(O)Me(η 1-dppe) in THF reacts with MeLi at -78°C to produce a novel complex [(η5-C5H5)Fe(CO)C-(O)Me](μ-η 1:η1-dppe)[(η4-MeC5H 5)Fe(CO)2] in which a dppe links two isomeric, methylated [(C5H5)Fe(CO)2] units, one end being in the form of (η5-C5H5)Fe(CO)C-(O)Me and the other end in the form of (η4-exo-MeC5H5)-Fe(CO)2. The X-ray structure of the title complex exhibits a dppe-bridged unsymmetrical pseudooctahedral Fe(II) / pseudosquare pyramidal Fe(0) complex without any metal-metal bonding. The embedded structural parameters of Fe(II) and Fe(0) centers give evidence of an Fe(II) smaller than Fe(0), as suggested by the Fe(II)-P length of 2.178(2) A? simultaneously present with that of Fe(0)-P, 2.212(1) A?. The shortening of 0.034 A? is significant as it represents a difference greater than 10 ESDs.