110428-32-5Relevant academic research and scientific papers
NEUARTIGE BASISCHE LIGANDEN FUER DIE HOMOGENKATALYTISCHE METHANOLCARBONYLIERUNG VII. 1,4-DIOXANYLMETHYLDIPHENYLPHOSPHAN ALS STEUERLIGAND BEI DER METHANOLHYDROCARBONYLIERUNG
Linder, Ekkehard,Sickinger, Anselm,Wegner, Peter
, p. C37 - C40 (1986)
The dioxane ligand Ph2PCH2C4H7O2, which is largely stable towards oxygen and hydrolysis, is obtained by reaction of ClCH2C4H7O2 with KPPh2 in THF.Concerning the hydrocarbonylation of methanol, the efficiency of this P,O ligand was proved using cobalt as a component of the catalyst and iodine as the promotor.While the conversion increased to 90percent, selectivity achieved a value of about 62percent.
Neuartige basische Liganden fur die homogenkatalytische Methanolcarbonylierung XVII. Dioxanylmethyldiorganylphosphane als Steuerliganden bei der Methanol(hydro)carbonylierung zu Acetaldehyd und Essigsaure
Lindner, Ekkehard,Sickinger, Anselm,Wegner, Peter
, p. 75 - 94 (1988)
The (ether-phosphane) ligands R2PCH2(1,4-diox) (1a-c) (R=Ph (a), Mess (b), Cy (c); diox=dioxane residue) and Ph2PCH2(1,3-diox) (2a) are obtained from the corresponding phosphides LiPR2 and 2-chloromethyl-1,4-dioxane and -1,3-dioxane, respectively, at -40 oC in ether.High pressure experiments can provide useful information on conversion and selectivity in the (hydro)carbonylation of methanol, if parameters like educt/catalyst ratio, effect of substituents of the ligands 1a-c, 2a, directed application of cobalt complexes, and composition of catalyst and synthesis gas are varied.The possibility that there is a cobalt-catalyzed (hydro)carbonylation of methanol to acetaldehyde and acetic acid cycle is explored.
BIPHASE REDUCTION OF HEPTANAL AND CYCLOHEXANONE BY SODIUM FORMATE CATALYZED BY ETHER-PHOSPHINE RUTHENIUM(II) COMPLEXES
Sabata, Stanislav,Vcelak, Jaroslav,Hetflejs, Jiri
, p. 127 - 136 (2007/10/02)
RuCl22 has efficiently catalyzed the reduction of cyclohexanone and heptanal by sodium formate in chlorobenzene-water, using cetylpyridinium bromide as the phase transfer catalyst.In both cases, the reduction was first order both in t
Novel Basic Ligands for the Homogeneous Catalytic Carbonylation of Methanol, XXVIII. - Synthesis, Properties and Fluxional Behavior of (Ether-Phosphine)palladium Complexes
Lindner, Ekkehard,Speidel, Robert,Fawzi, Riad,Hiller, Wolfgang
, p. 2255 - 2260 (2007/10/02)
Cl2Pd(COD) (1) (COD = 1,5-cyclooctadiene) reacts with 1 equiv. of the (ether-phosphine) ligand Ph2P-D (2a-c) to give the dimeric complexes 2 (3a-c) (P-D = η1-P-coordinated).According to the field-desorption mass spectra which show only one peak for the monomeric moieties ClPd(Ph2P-D), 3a-c have a very weak Pd2Cl2 bridge. trans-Cl2Pd(Ph2P-D)2 (4a-c) is obtained either from 3a-c and 2a-c by cleaving the Pd2Cl2 bridge or from 1 and 2 equiv. of the ligands 2a-c. 4c crystallizes in the monoclinic spacegroup P21/c with Z = 2.AgClO4 selectively abstracts one Cl- ligand from 4a-c which results in the formation of the cationic complexes D)(Ph2P-D)PdCl>+ (5a-c) (PD = η2-D,P-coordinated) containing one chelated and one η1-P-bonded (ether-phosphine) ligand. 5a-c show fluxional behavior which is demonstrated by temperature-dependent 31P-NMR investigations.The coalescence points have been determined and are at 253 (5a), 303 (5b), and 283 K (5c).The activation enthalpies ΔGexcit. are estimated at 48, 58, and 54 kJ/mol.The abstraction of the second Cl- ligand from 5a-c succeeds only in the presence of AgSbF6 yielding the dicationic bis(chelate) complexes D)2Pd>2+ (6a-c).The latter are also obtained from 4a-c and AgSbF6.The hydrogenating properties of 3a-c and 4a-c toward 1-hexyne are investigated in comparison with trans-Cl2Pd(Ph2PCH2CH2CH3)2.
