91533-65-2Relevant academic research and scientific papers
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.
Novel Basic Ligands for the Homogeneous Catalytic Homologation of Methanol to Ethanol, II. Synthesis and Complex Chemical Behaviour of Potential Bi- and Tridentate P-N and P-O Containing Chelate Ligands
Lindner, Ekkehard,Rauleder, Hartwig,Scheytt, Christoph,Mayer, Hermann August,Hiller, Wolfgang,et al.
, p. 632 - 642 (2007/10/02)
Tridentate P-N and P-O ligands of the type RP(XC5H4N)2 (1a, b, a', b') and PhP(CH2C4H7O)2 (1c'') are obtained by reaction of RPCl2 with 2-hydroxy- and 2-aminopyridine and Li2PPh with tetrahydrofurfuryl chloride, respectvely.In a similar way the potential bidentate ligand Ph2PCH2C4H7O (2c'') is formed by the action of LiPPh2 on ClCH2C4H7O.Potential tridentate ligands as RP(C4H3O)2 (3a'''-c''') with two furyl-phosphorus bonds can be isolated from RPCl2 and furyllithium.The complex chemical behaviour towards Mo(CO)6 or carbonyl derivatives of chromium was elucidated for 2c''' and 3a'''-c''', resulting in the formation of (OC)5MoPPh2CH2C4H7O (4c'') and trans-(OC)4Cr2 (5a'''-c'''), respectively.In the case of 5a''' an X-ray investigation proved 3a'''-c''' to be only monodentate P-ligands. 5a''' crystallizes in the monoclinic space group P21/c with Z = 2. 1c'' is the most versatile species within this series and functions probably as tri-, bi- and monodentate P-O ligand.With 1c'' and 3c''' some homologation experiments of methanol at 200 deg C and 304 bar synthesis gas pressure were carried out. - Key words: Tri- and Bidentate P-N and P-O Ligands, Complexes of Cr, Mo, Structure of trans-(OC)4Cr2, NMR Spectra
