Notes. Unsymmetrical bis(phosphorus) compounds: synthesis of unsymmetrical ditertiary phosphines, phosphine oxides, and diquaternary phosphonium salts

Benn, Florence; Briggs, Josie C.; McAuliffe, Charles A.

doi:10.1039/dt9840000293

Cited by 24 publications

(12 citation statements)

References 2 publications

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“…General: All reactions were carried out in Schlenk tubes under an atmosphere of dinitrogen by using anhydrous solvents purified according to standard procedures. The compounds 1‐[(4′‐iodophenyl)methyl]imidazole,181‐bromopropyl‐3‐triphenylphosphonium bromide19 and [{Rh(μ‐Cl)(cod)} 2 ],20 and [{Ir(μ‐Cl)(cod)} 2 ]21 were prepared according published procedures. All chemicals were purchased from commercial sources and used as received.…”

Section: Methodsmentioning

confidence: 99%

Synthesis, Cellular Uptake and Biological Activity Against Pathogenic Microorganisms and Cancer Cells of Rhodium and Iridium N‐Heterocyclic Carbene Complexes Bearing Charged Substituents

et al. 2013

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Four new N‐heterocyclic carbene (NHC) rhodium and iridium complexes decorated with anionic or cationic pendant groups to increase their water solubility and biological activity have been synthesised and characterised. The lipophilicity of the complexes was determined and the complexes that contained cationic phosphonium groups can be considered delocalised lipophilic cations (DLCs). All complexes were tested for their antibacterial, antiparasitic and anticancer activity, with only the phosphonium‐functionalised complexes showing moderate to high activity, whereas the exchange of metal from rhodium to iridium had a negligible effect. Most promising was the activity on Trypanosoma brucei, with IC50 values in the range of 150–400 nM and a selectivity index (SI) of up to 50. General toxicity on mammalian cell lines was a general problem, though, and needs to be mitigated in future work. Cellular uptake studies clearly confirmed that the cationic phosphonium groups facilitated uptake, which was linked with higher biological activity.

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Section: Methodsmentioning

confidence: 99%

Synthesis, Cellular Uptake and Biological Activity Against Pathogenic Microorganisms and Cancer Cells of Rhodium and Iridium N‐Heterocyclic Carbene Complexes Bearing Charged Substituents

et al. 2013

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“…In the 13 C-NMR spectra, the d( 13 C) values of PNCH 3 The platinum complex 5 is a powder which is almost insoluble in common solvents, so that no 1 Hand 13 C-NMR spectra are available. The d( 31 P) value could be obtained after extended pulsing for more than 2 hours.…”

Section: Characterization Of 2±6mentioning

confidence: 99%

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Fei

Thönnessen

Jones

et al. 2000

Z. anorg. allg. Chem.

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Dedicated to Professor Manfred Fild on the Occasion of his 60 th Birthday.Abstract. The reaction of the bis-chlorophosphines 1 a±1 d with bis(2-chloroethyl)amine hydrochloride in the presence of triethylamine and with various trimethylsilylamines led to a new class of bis-phosphorus ligands 2 a±2 c and 3 a±3 g. 31 P-NMR studies suggested that the bis-phosphorus ligands undergo rotation reactions about the alkyl bridge in polar solvents. Compounds 2 a±2 c showed initially only one sharp singlet each in their 31 P-NMR spectra. After a few days at room temperature, two signals were observed. Similar results were observed for 3 a±3 g. In the solid state, the two phosphorus atoms in 2 c are not equivalent, as was confirmed by the observation of two signals in the solid state 31 P-NMR spectrum. Oxidation reactions of 2 a±2 c by the hy-drogen peroxide-urea 1 : 1 adduct (NH 2 ) 2 C(:O)´H 2 O 2 led to the formation of the corresponding phosphoryl compounds 4 a±4 c. Reaction of 2 a and 3 a with Pt[COD]Cl 2 (COD = 1.5-Cyclooctadiene) furnished the complexes 5 and 6. The NMR spectra suggested that the two chlorine atoms are in cis position. X-ray structure analyses were conducted for 2 a, which exhibits twofold symmetry; 2 c, which is linked into dimers by hydrogen bonds C±H´´´O; and 6, confirming the cis configuration.Alkylverbru È ckte Bis-Phosphoryl-Verbindungen mit zwei 1,3,2-Benzodiazaphosphorinon-Einheiten; Oxidation, Komplexierung und Ro È ntgenstrukturanalyse ausgewa È hlter Verbindungen Inhaltsu È bersicht. Die Umsetzung der Bis-Chlorphosphine 1 a±1 d mit Bis(2-Chlorethyl)amin-Hydrochlorid in Gegenwart von Triethylamin und mit verschiedenen Trimethylsilylaminen fu È hrte zu der neuen Klasse der Bis-Phosphor-Verbindungen 2 a±2 c und 3 a±3 g. 31 P-NMR-Untersuchungen zeigten fu È r diese Verbindungen in polaren Lo È sungsmitteln das Vorliegen von Rotationsprozessen um die Alkylbru È cke. Die Verbindungen 2 a±2 c zeigten 31 P-NMR-spektroskopisch anfangs jeweils nur ein scharfes Singulett, das sich nach einigen Tagen Lagerung bei Raumtemperatur in zwei Signale gleicher Intensita È t umwandelte. Øhnliches Verhalten wurde auch fu È r 3 a±g beobachtet. Im festen Zustand sind die zwei Phosphoratome in 2 c nicht a È quivalent, was durch das Auftreten von zwei Signalen im Feststoff-31 P-NMR-Spektrum nachgewiesen wurde. Oxidationsreaktionen an 2 a±2 c durch das Wasserstoffperoxid-Harnstoff-1 : 1-Addukt (NH 2 ) 2 C(:O)´H 2 O 2 fu È hrte zur Bildung der entsprechenden Phosphorylverbindungen 4 a±4 c. Die Umsetzung von 2 a und 3 a mit Pt[COD]Cl 2 (COD = 1.5-Cyclooctadiene) lieferte die Platinkomplexe 5 und 6. Die NMR-Spektren zeigten, daû die zwei Chloratome in den Verbindungen cis-orientiert sind. Ro È ntgenstrukturanalysen wurden durchgefu È hrt fu È r 2 a, das zweiza È hlige Symmetrie zeigt, fu È r 2 c, das durch Wasserstoffbru È ckenbindungen C±H´´´O zu Dimeren verbunden ist, und fu È r 6, fu È r das die cis-Konfiguration besta È tigt wird.

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“…Organic solvents were purified using standard procedures and fresh distilled prior to use. PMePh 2 , PMe 2 Ph and PEt 3 were obtained according to the literature procedures and stored at –30 °C.…”

Section: Methodsmentioning

confidence: 99%

Direct Phosphination of Ferrocenium Ion with Tertiary Phosphines by the Mechanism of Oxidative Nucleophilic Substitution

et al. 2018

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Ferrocenium salts [(C5H5)2Fe]X (X = BF4, PF6) (I+·) react with tertiary phosphines PR3 (PMe3, PEt3, PnBu3, PMe2Ph, and PMePh2) in dichloromethane at room temperature to form a mixture of the corresponding ferrocenylphosphonium salts [(C5H5)FeC5H4PR3]X (III), ferrocene (I), and phosphonium salts [HPR3]X. The same reaction was carried out in an electrochemical cell as the electrolysis of a solution of ferrocene and phosphine in dichloromethane at the oxidation potential of ferrocene. Possible reaction pathways for phosphination of ferrocenium ion were studied by DFT at the M06‐L/6‐311++G(d,p) theory level. The experimental and theoretical studies of this reaction suggest it to proceed according to the Scheme of oxidative nucleophilic substitution of hydrogen in I+· including the following steps: a) nucleophilic exo addition of a phosphine to the cyclopentadienyl ring of I+· to form the radical cation adduct [(η5‐C5H5)Fe·(η4‐C5H5–+PR3)]X (II+·); b) redox reaction of the initial adduct II+· with the starting ferrocenium salt I+· to result in ferrocene (C5H5)2Fe (I) and iron phosphoniocyclopentadiene dication [(η5‐C5H5)Fe+(η4‐C5H5–+PR3)](X)2 (II2+) where the Csp3–H bond is involved in the agostic interaction with the metal atom; and c) deprotonation of the Csp3–H bond in II2+ by the starting phosphine to form III. The relation between the data obtained and current concepts of C–H functionalization in transition metal arene and cyclopentadienyl complexes is discussed.

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Notes. Unsymmetrical bis(phosphorus) compounds: synthesis of unsymmetrical ditertiary phosphines, phosphine oxides, and diquaternary phosphonium salts

Cited by 24 publications

References 2 publications

Synthesis, Cellular Uptake and Biological Activity Against Pathogenic Microorganisms and Cancer Cells of Rhodium and Iridium N‐Heterocyclic Carbene Complexes Bearing Charged Substituents

Synthesis, Cellular Uptake and Biological Activity Against Pathogenic Microorganisms and Cancer Cells of Rhodium and Iridium N‐Heterocyclic Carbene Complexes Bearing Charged Substituents

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Direct Phosphination of Ferrocenium Ion with Tertiary Phosphines by the Mechanism of Oxidative Nucleophilic Substitution

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