Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

Abstract

Ion pairs containing N-substituted derivatives of 1,3,5-triaza-7-phosphaadamantane (pta-R; R= benzyl, butyl, hexyl) as cations and monosulfonated triphenylphosphine (mtppms) as anion were synthetized and characterized (including X-ray diffraction, too). These ion pairs act as bidentate phosphorus ligands in reactions with [(η 6 -C 10 H 14 )RuCl 2 ] 2 , yielding mononuclear or dinuclear half sandwich Ru(II) complexes. A bisphosphine 3 of good watersolubility was synthesized in reaction of pta with 1,4-bis(chloromethyl)benzene and used for the synthesis of the water-soluble dinuclear complex [{(η 6 -C 10 H 14 )RuCl 2 } 2 (μ-3)]Cl 2 .

In vitro Cytotoxicity of Half‐Sandwich Platinum Group Metal Complexes of a Cationic Alkylated Phosphaadamantane Ligand

“…31 P{ 1 H} NMR spectroscopy of 1 confirmed the presence of a single phosphorus species as only a singlet was observed in the spectrum at δ –81.95 ppm. These spectroscopic data are in accordance with assignments made to a similar binuclear ligand system 26. HR‐ESI‐MS displayed a mass‐to‐charge ( m / z ) signal for the trimeric ligand 1 as [M – 3Cl] 3+ .…”

“…A doublet signal was observed for complex 2 , δ –22.89 ppm ( J Rh‐P = 151 Hz), which indicates that the phosphorus atom is coordinated to the NMR spin active Rh III metal, and singlet signals observed for complex 3 , δ = –46.52 ppm, and complex 4 , δ = –23.03 ppm. Similar shifts for complex 4 were observed in a dinuclear Ru II system prepared by Kathó and co‐workers 26. Complexes 2 – 4 display m / z signals corresponding to [M – 5Cl – 2H] 3+ .…”

“…Kathó and co‐workers prepared a water‐soluble monodentate dinuclear Ru II complex, based on an alkylated PTA ligand, with relative ease 26. This system involved quaternization of PTA with 1,4‐bis(chloromethyl)benzene.…”

Diaquabis(pyridine-2-carboxylato-κ2N,O)zinc dimethylformamide hemisolvate

“…For background to polydentate ligands, see: Udvardy et al (2013); Groni et al (2008); Golenya et al (2011);Ma et al (2009). For related structures, see : Chen & Hu (2011);Li et al (2008); Lumme et al (1969); Takenaka et al (1970); Uggla et al (1969).…”

“…The combination of pyridyl and carboxyl groups in a single bridge-type ligand results in highly interconnected networks and gives limitless possibilities for increased network stability (Udvardy et al, 2013;Groni et al, 2008;Golenya et al 2011). The COO -group and the nitrogen atom in Hpic have strong coordination abilities and multiple coordination modes (Ma et al, 2009).…”