Synthesis of sulfated mono- and ditertiary phosphines, complex chemistry and catalysis

Gulyás, H; Dobó, A; Bakos, J
May 2001
Canadian Journal of Chemistry;May2001, Vol. 79 Issue 5/6, p1040
Academic Journal
Cyclic and bicyclic sulfates have been prepared from commonly available alcohols. Nucleophilic cleavage of the cyclic sulfates affords a new type of water-soluble mono- and ditertiary phophines bearing -OSO[sub 3] Li groups in distinguished positions in the molecular framework. Both phosphines have amphiphilic character. Reactions of the chiral 2 and the dppp analogue 5 with [Rh(COD)Cl][sub 2] and Pt(PhCN)[sub 2] Cl[sub 2] provide novel zwitterionic complexes. Rhodium complexes of 2 and 5 have been successfully applied in liquid biphasic hydroformylation of styrene and octene-1. When the rhodium complex of 5 was used as catalyst in hydroformylation of styrene, less then 4 ppm rhodium could be detected in the organic phase.Key words: cyclic sulfates, water soluble phosphines, amphiphilic character, Rh complexes, Pt complexes, hydroformylation.On a préparé des sulfates cycliques et bicycliques à partir d'alcools disponibles facilement. Le clivage nucléophilique des sulfates cycliques conduit à la formation d'un nouveau type de phosphines mono- et ditertiaires, solubles dans l'eau, portant des groupes -OSO[sub 3] Li dans des positions définies du squelette moléculaire. Les deux types de phosphines présentent un caractère amphiphilique. Les réactions du [Rh(COD)Cl][sub 2] et du Ph(PhCN)[sub 2] Cl[sub 2] avec composé chiral 2 et de son analogue à la dppp, 5, conduisent à la formation de nouveaux complexes zwitterioniques. On a pu appliquer avec succès les complexes 2 et 5 du rhodium à l'hydroformylation biphasique liquide du styrène et de l'oct-1-ène. Quand on a utilisé le complexe de rhodium 5 comme catalyseur dans l'hydroformylation du styrène, on n'a détecté que quatre ppm de rhodium dans la phase organique.Mots clés : sulfates cycliques, phosphines solubles dans l'eau, caractère amphiphilique, complexes du rhodium, complexes du platine, hydroformylation.[Traduit par la Rédaction]


Related Articles

  • Study of the hydroformylation of 2,5-dihydrofuran catalyzed by rhodium diphosphine complexes. Río, Inmaculada del; van Leeuwen, Piet WNM; Claver, Carmen // Canadian Journal of Chemistry;May2001, Vol. 79 Issue 5/6, p560 

    Rhodium diphosphine systems, including chiral ones, were used as catalyst precursors for the hydroformylation of 2,5-dihydrofuran. The effect of the reaction conditions and the bite angle on the activity and selectivity of the reaction were studied. The solution structures of the species present...

  • SYNTHESIS AND COORDINATION CHEMISTRY OF THIOPHENOL-BASED HETERODONOR LIGANDS CONTAINING P,S, As,S AND P,SAs DONOR ATOMS. Sárosi, Imola; Silaghi-Dumitrescu, Luminița; Hey-Hawkins, Evamarie // Macedonian Journal of Chemistry & Chemical Engineering;2013, Vol. 32 Issue 1, p1 

    This review article describes the synthesis and coordination chemistry of three types of thiophenol-based heterodonor ligands containing tertiary phosphine and/or arsine groups in combination with sulfur. Phenylthio(diphenyl)phosphine and -arsine ligands, EPh2(SPh) (E = P, As), incorporate an...

  • Hydrosilylation of Vinylsiloxanes with Hydrosiloxanes in the Presence of Thermo- and Photoactivated Platinum(II) Phosphine Complexes. de Vekki, D. A.; Skvortsov, N. K. // Russian Journal of General Chemistry;Feb2004, Vol. 74 Issue 2, p197 

    Catalytic properties of thermo- and photoactivated platinum complexes [Pt(R2R'X)2Cl2] (X = P, R = Me, R' = Ph; X = P, As, Sb, R = R' = Ph or Bu) in hydrosilylation of vinylsiloxanes with hydrosiloxanes were studied. The neutral ligands were ranked in terms of their effect on the activity of the...

  • Alkenylphosphines: Applications in Synthesis, Catalysis and Coordination Chemistry. Julienne, D.; Toulgoat, F.; Delacroix, O.; Gaumont, A.-C. // Current Organic Chemistry;Jul2010, Vol. 14 Issue 12, p1195 

    Alkenylphosphines are compounds of great interest in view of their structures. The most interesting feature is the carbon-carbon double bond, which is directly linked to the phosphorus atom. Nucleophilic addition or cycloaddition reactions can take place at this unsaturation, which can also be...

  • Regioselective upper-rim functionalizations of calix[4]arene by diphenylphosphino groups. Gagnon, Jonathan; Vézina, Martin; Drouin, Marc; Harvey, Pierre D // Canadian Journal of Chemistry;Oct2001, Vol. 79 Issue 10, p1439 

    The regioselective upper-rim functionalization of calix[4]arene have been performed to prepare all the multisubstituted diphenylphosphine derivatives. In addition, the X-ray structures of 5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetra-n-propoxycalix[4]arene and...

  • Tetraacetatodirhodium(II) complexes with tris(methoxyphenyl)phosphines, their reactivity, structure, and antitumor activity. Pruchnik, Florian P; Starosta, Radoslaw; Ciunik, Zbigniew; Opolski, Adam; Wietrzyk, Joanna; Wojdat, Elzbieta; Dus, Danuta // Canadian Journal of Chemistry;May2001, Vol. 79 Issue 5/6, p868 

    Reactions of [Rh[sub 2] (µ-OAc)[sub 4] (H[sub 2] O)[sub 2] ] ([1·(H[sub 2] O)[sub 2] ]) with tris(3-methoxyphenyl)phosphine at 1:1 and 1:2 molar ratios yield, first, the appropriate adducts: [1·(H[sub 2] O){P(C[sub 6] H[sub 4] -3-OMe)[sub 3] }] and [1·{P(C[sub 6] H[sub 4] -3-OMe)[sub...

  • Synthetic and solution calorimetric investigations of chelating phosphine ligands in Ru(allyl)[sub 2] (PP) complexes (PP = diphosphine). Smith, Jr., Dale C; Cadoret, Jérémie; Jafarpour, Laleh; Stevens, Edwin D; Nolan, Steven P // Canadian Journal of Chemistry;May2001, Vol. 79 Issue 5/6, p626 

    Reaction enthalpies of (COD)Ru(allyl)[sub 2] (COD = η[sup 4] -1,5-cyclooctadiene; allyl = 2-methylpropenyl) with a series of bidentate phosphines (dppm, dppf, dppe, dppb, dppp, depe, dmpe) have been measured by anaerobic solution calorimetry. The relative stability of the resulting complexes...

  • Noncatalytic Regio- and Stereoselective Addition of Secondary Phosphines to Cyanoacetylenic Alcohols. Arbuzova, S. N.; Shaikhutdinova, S. I.; Gusarov, N. K.; Nikitin, M. V.; Mal�kina, A. G.; Sukhov, B. G.; Bogdanova, M. V.; Trofimov, B. A. // Russian Journal of General Chemistry;Apr2005, Vol. 75 Issue 4, p514 

    Secondary phosphines regio- and stereoselectively add to 4-hydroxy-4-methyl-2-pentynenitrile, a typical and available representative of cyanoacetylenic alcohols, without catalyst at room temperature (THF, 3 h) to form ( Z)-3-[dialkyl(aryl) phosphino]-4-hydroxy-4-methyl-2-pentenenitriles in...

  • The Synthesis of Tertiary and Secondary Phosphines and Their Applications in Organic Synthesis. Honaker, Matthew T.; Hovland, Jason M.; Salvatore, Ralph Nicholas // Current Organic Synthesis;Jan2007, Vol. 4 Issue 1, p31 

    This review focuses on a literature survey of the uses and the different approaches for the syntheses of tertiary and secondary phosphines. In addition, their applications in organic synthesis are briefly overviewed along with basic methods for their preparation and physical properties are also...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics