- DIPHOSPHINE DERIVATIVES. Part VIII. Tetraphenyldiphosphine dioxide and tetraphenyldiphosphine disulphide: structure and skeletal vibrations. Preparation of diphenyphosphinodiselenoic anhydroselenide, Ph2P(Se)SeP(Se)Ph2
-
The X-ray powder diffraction pattern for tetraphenyldiphosphine dioxide Ph2P(O)P(O)Ph2 can be satisfactorily indexed on the assumption that the compound is isomorphous with tetraphenyldiphosphine disulphide.Calculated crystal data for the dioxide are: monoclinic, P21/c, a = 9.44(1), b = 15.62(3), c = 13.87(3) Angstroem, β = 98.0(1)0 Z = 4.The P-P stretch is assigned in the Raman spectrum of the disulphide at 536 cm-1 and in dioxide at the usually high frequency of 601 cm-1.The reaction of tetraphenyldiphosphine with KSeCN in acetonitrile leads to oxidation of the phosphorous and selenium insertion into the P-P bond, yielding Ph2P(Se)SeP(Se)Ph2, diphenylphosphinodiselenoic anhydroselenide, previously only identified in solution.
- Blake, A.J.,McQuillan, G. P.,Oxton, I. A.,Troy, D.
-
-
Read Online
- Reaction of quinoline-5,8-diones with selected charged phosphorus nucleophiles
-
The redox reactivity of the two quinoline-5,8-dione derivatives2-methyl-5, 8-dioxo-5,8-dihydroquinoline-7-amine (2a) and N-(2-methyl-5,8-dioxo-5,8- dihydroquinolin-7-yl)acet-amide (2b)has been demonstrated by their reaction with negatively charged three-c
- Nycz, Jacek E.,Malecki, Grzegorz,Chikkali, Samir,Hajdok, Imre,Singh, Priti
-
-
Read Online
- New look into the synthesis of polyhalogenoarylphosphanes
-
The present study shows new aspects of the synthesis of polyhalogenoarylphosphanes. The sterically hindered anions Ph(R)P-Y- (1a-c, Y = O, lone pair; R = Ph, But) have been used to show the complexity of the reaction between phosphorus nucleophiles and hexahalogenobenzenes or 9-bromofluorene (E3). The Ph(But)P-O-(1a) anion reacts with hexachlorobenzene (E1), hexafluorobenzene (E2), or E3 to give Ph(R)P(O)X (4a-c, X = F, Cl, Br) with the release of the corresponding carbanion as a nucleofuge, followed by side reactions. In contrast, the lithium phosphides Ph(R)PLi (1b,c) react with hexahalogenobenzenes to give the corresponding diphosphanes 5a,b as the main product and traces of P-arylated products, i.e., Ph(R)P-C6X 5 (10a,b, X = Cl, F). Unexpectedly, Ph(But)PLi (1b) reacts with an excess of 9-bromofluorene to give only halogenophosphane Ph(Bu t)P-X. Taylor & Francis Group, LLC.
- Nycz, Jacek E.
-
experimental part
p. 2605 - 2612
(2010/08/06)
-
- New approaches to the synthesis of diphosphine dioxides and hypophosphoric acid esters
-
An union >P-O- has been applied as an efficient synthetic precursor of four coordination compounds of the R2P(O)-(O)PR 2 type, namely diphosphine dioxides (R = alkyl, aryl) as well as hypophosphoric acid esters (R = alkoxy, aryloxy), in a one-pot reaction. Furthermore, there were elaborated some mechanistic aspects of the origin of the >P(O)-O-(O)PP-O- and >P(O)X (X= Cl, Br) electrophiles. Attention is focused on the synthesis of the >P(O)-(O)P compounds.
- Nycz, Jacek E.,Musiol, Robert
-
p. 310 - 316
(2007/10/03)
-
- (2,4,6-Trimethylbenzoyl)diphenylphosphine oxide photochemistry. A direct time-resolved spectroscopic study of both radical fragments
-
The photochemistry of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (1) has been investigated using time-resolved infrared (TRIR) and time-resolved UV spectroscopy (laser flash photolysis (LFP)), in addition to conventional photochemical steady-state te
- Sluggett, Gregory W.,Turro, Claudia,George, Michael W.,Koptyug, Igor V.,Turro, Nicholas J.
-
p. 5148 - 5153
(2007/10/02)
-
- Reactions of P_Cl compounds in presence of SMI2
-
Conversion of P-Cl to P-H and P-C bonds are induced by SmI2 in mild conditions. Especially phosphines oxides and sulfides are obtained in good yields.
- Sasaki, Mitsuru,Collin, Jacqueline,Kagan, Henri B.
-
p. 2493 - 2496
(2007/10/02)
-
- ELECTRON-TRANSFER PROCESSES. PART 40. REACTION OF ALKYL RADICALS WITH DIPHENYLPHOSPHIDE ANION
-
The anion Ph2P- (K+, 18-crown-6) reacts with t-BuHgCl in HMPA to form Ph2PCMe3 by a free radical chain mechanism.In Me2SO, PhP(O)CMe3 is produced.Reaction of Ph2P- with PhCOCH2HgCl yields the oxidative dimerization product isolable from HMPA but readily converted to Ph2P(O)P(O)Ph2 in Me2SO.
- Russell, Glen A.,Khanna, Rajive K.
-
p. 271 - 274
(2007/10/02)
-
- Studies on the Occurence of Hydrogen Transfer, 67. Enediol Diesters by Acylating Electroreductive Dimerization of Acyl Chlorides with Lithium Amalgam
-
Aromatic, aliphatic, and aromatic-aliphatic acyl chlorides (and anhydrides) are transformed by lithium amalgam (Li/Hg) to cis- and/or trans enediol diesters 1-10 (acylating reductive dimerization), mostly in ca. 70percent yields.The influence of the solvent on the reaction course is investigated.Starting from 2,2'-biphenyldicarbonyl dichloride, the phenanthrene 7 is formed; phthalide 8 is the reaction-product using phthaloyl dichloride as starting material.Diphenylphosphinyl chloride is reduced by Li/Hg to tetraphenyldiphosphane dioxide (15).A reaction mechanism for the acylating reductive dimerization is proposed on the basis of the halve-wave potentials determined for 12 acyl chlorides and four 1,2-diketones.The latter are intermediates in the acylating reductive dimerization of the acyl chlorides.Enediol diesters are obtained starting from 1,2-diketones and Li/Hg in the presence of acyl chlorides.Trimethylsilyl chloride is unsuitable as a trap for the enediols; it is preferentially reduced at the Li/Hg interface.Tetrahydrofuran as solvent is transformed to RC(O)O-4-Cl by a known ring-opening acylation reaction in the presence of Lewis acids (LiCl or ZnCl2) formed by the decomposition of Li/Hg and Zn/Hg.
- Horner, Leopold,Dickerhof, Karlheinz
-
p. 1603 - 1614
(2007/10/02)
-
- The Behaviour of Oxalyl-bis(diphenylphosphane) Towards Oxygen
-
In dependence of the solvent, oxalyl-bis(diphenylphosphane) (1) is oxidized with molecular oxygen either in a radical or an ionic mechanism to give - via the radicals PPh2 and the recombination products 2 (3) - the oxide 2 (4) and 2O (6), respectively.In both cases CO and CO2 are eliminated in nearly equal amounts. - Keywords: Oxidation of Oxalyl-bis(diphenylphosphane), Mechanism
- Lindner, Ekkehard,Kern, Herbert
-
p. 790 - 792
(2007/10/02)
-