28240-70-2Relevant academic research and scientific papers
Gold(I) chloride adducts of 1,3-bis(di-2-pyridylphosphino)propane: Synthesis, structural studies and antitumour activity
Humphreys, Anthony S.,Filipovska, Aleksandra,Berners-Price, Susan J.,Koutsantonis, George A.,Skelton, Brian W.,White, Allan H.
, p. 4943 - 4950 (2007)
The novel water soluble bidentate phosphine ligand 1,3-bis(di-2- pyridylphosphino)propane (d2pypp) has been synthesized by a convenient route involving treatment of 2-pyridyllithium with Cl2P(CH 2)3PCl2 and isolation in crystalline form as the hydrochloride salt. The synthesis of the precursor Cl2P(CH 2)3PCl2 has been optimized by the use of triphosgene as the chlorinating agent. The 2: 1 and 1: 2 AuCl: d2pypp adducts have been synthesized and characterized by NMR spectroscopy and single crystal X-ray studies, and shown to be of the form (AuCl)2(-d2pypp-P, P′) and [Au(d2pypp-P,P′)2]Cl(·3.75H2O), respectively. The latter is more lipophilic than analogous 1: 2 adducts of gold(i) chloride with the diphosphine ligands 1,2-bis(di-n-pyridylphosphino) ethane (dnpype) for n = 2, 3 and 4, based on measurement of the n-octanol-water partition coefficient (log P = -0.46). A single crystal structure determination of the 1: 2 Au(i) complex of the 3-pyridyl ethane ligand shows it to be of the form [Au(d3pype-P,P′)2]Cl·5H2O. The in vitro cytotoxic activity of [Au(d2pypp)2]Cl was assessed in human normal and cancer breast cells and selective toxicity to the cancer cells found. The significance of these results to the antitumour properties of chelated 1: 2 Au(i) diphosphine complexes is discussed. This journal is The Royal Society of Chemistry.
Catalytic activity of cationic diphospalladium(II) complexes in the alkene/CO copolymerization in organic solvents and water in dependence on the length of the alkyl chain at the phosphine ligands
Lindner, Ekkehard,Schmid, Markus,Wald, Joachim,Queisser, Joachim A.,Gepr?gs, Michael,Wegner, Peter,Nachtigal, Christiane
, p. 173 - 187 (2000)
A series of diphos ligands CH2(CH2PR2)2 (1a-x) (a-g: R=(CH2)nOH, n=1, 3-8; h-k: R=(CH2)nCH(CH2OH)2, n=3-6; l-u: R=CnH2n+1, n=1-8, 10, 14; v-x: R=CH(CH3)2, (CH2)2CH(CH3)2, (CH2)3CH(CH3)2, (Scheme 1), provided with functionalities of different polarity, was prepared photochemically by hydrophosphination of the corresponding 1-alkenes with H2P(CH2)3PH2 or reaction of Grignard reagents with Cl2P(CH2)3PCl2. The water-soluble palladium complexes [(R2P(CH2)3PR2)Pd(OAc)2] (2a-k) were obtained by reaction of Pd(OAc)2 with the ligands 1a-k in ethanol-acetonitrile. Treatment of PdCl2(NCC6H5)2 with 1l-x afforded the dichloropalladium(II) complexes [(R2P(CH2)3PR2)PdCl2] (3l-x). Upon chloride abstraction with AgBF4 in dichloromethane-acetonitrile the dicationic palladium(II) complexes [(R2P(CH2)3PR2)Pd(NCCH 3)2][BF4]2 (4l-x) are formed. The structure of 4n (R=n-Pr) was investigated by an X-ray structural analysis. In particular the water-soluble complexes 2c-k proved to be highly active in the carbon monoxide/ethene copolymerization under biphasic conditions (water-toluene). In the presence of an emulsifier and methanol as activator the catalytic activity increased by a factor of about three. Also higher olefins could be successfully incorporated into the copolymerization with CO and the terpolymerization with ethene and CO. The catalytic activity of the dicationic complexes 4l-x in the propene or 1-hexene/CO copolymerization strongly depends on the length of the alkyl chain R. At 25°C a maximum is achieved in the case of 4q (R=nHex) which is five times more active than the corresponding catalyst with the dppp-ligand. This maximum is shifted to 4t (R=n-C10H21) if the temperature is raised to 60°C. The 1-alkene/CO copolymers are distinguished by their regioregular microstructure and their ultra high molecular weights. Compared to the sulfonated dppp-SO3 catalyst the water-soluble complexes 2c,e,f,h are responsible for a higher 1-hexene incorporation in the terpolymerization of ethene with 1-hexene and CO.
A new method for the synthesis of dichlorophosphines
Tavtorkin, Alexander N.,Toloraya, Sofia A.,Nifant'Ev, Eduard E.,Nifant'Ev, Ilya E.
supporting information; experimental part, p. 824 - 825 (2011/03/18)
A new method for the synthesis of alkyldichlorophosphines by chlorination of alkylphosphines with phosphorus pentachloride under mild conditions is described.
Highly fluorous bidentate phosphines
Berven, Bradley M.,Koutsantonis, George A.
experimental part, p. 2626 - 2630 (2009/04/06)
The reaction of tetrachlorodiphosphines [Cl2P(CH 2)nPCl2; n = 2-4] with fluorous aromatic precursors 4-bromo(perfluorohexyl)benzene and 4-(perfluorohexyl)phenol gave a series of fluorous-tagged diphosphines [(p-C6F13C 6H4)2P(CH2)nP(C 6H4C6F13-p)2; n = 2-4] and a new diphosphonite [(p-C6F13C6H 4O)2P(CH2)3P(OC6H 4C6F13-p)2]. The improved synthesis of 1,3-bis(dichlorophosphino)propane (dcpp), involved the facile chlorination of the corresponding primary phosphine with triphosgene. Fluorinated diimines RN=C(CH3)C(CH3)=NR, where R = p-C6H 4C6F13 or P-C6H4C 8F17 have also been prepared, and were found to be air-stable alternatives to the highly air-sensitive phosphorus-containing ligands. All compounds were characterised by a variety of techniques including NMR, IR, MS and microanalysis. The successful reduction of the phosphine-oxides [(p-C6F13C6H4)2P(O) (CH2)nP(O)(C6H4C6F 13-p)2; n = 2,3] with phenylsilane is also presented. Georg Thieme Verlag Stuttgart.
