Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung

Lindner, Ekkehard; Glaser, Erhard; Mayer, Hermann A.; Wegner, Peter

doi:10.1016/0022-328x(90)85518-4

Cited by 10 publications

(16 citation statements)

References 31 publications

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“…IR data were obtained on a Bruker IFS 48 FT-IR spectrometer. 31 P{ 1 H} NMR spectra were recorded at 32.391 MHz on a Bruker AC 80, 13 C{ 1 H} NMR spectra at 62.89 MHz (100.622 MHz) on a Bruker AC 250 (AMX 400). The 13 C and 31 P CP MAS solid state NMR spectra were recorded on a Bruker ASX 300 multinuclear spectrometer with a 4 mm probehead.…”

Section: Methodsmentioning

confidence: 99%

“…The rotor was filled with the sample, using the normal Schlenk technique. Frequencies and standards: 31 45 Typically, contact times Tc of 4 ms ( 29 Si), 2 ms ( 31 P), and 2 ms ( 13 C), respectively, were applied to routine CP MAS NMR spectra. Peak deconvolution of the spectra were performed with the Bruker software GLINFIT using Gaussian line shapes.…”

Section: Methodsmentioning

confidence: 99%

“…The hydrolysis and polycondensation of silicon alkoxides provided with a transition metal functionalized organic spacer R is of particular interest, because it allows the preparation of transition metal modified polymers as stationary phases with a wide variety of anchored metal complexes. 6,20-25 The resulting polymers are functionalized with immobilized homogeneous catalysts. ,− …”

Section: Introductionmentioning

confidence: 99%

“…6,[20][21][22][23][24][25] The resulting polymers are functionalized with immobilized homogeneous catalysts. 21,[26][27][28][29][30][31][32][33][34] The characteristics of the matrix can be varied by the simultaneous cocondensation of D, T, or Q type alkoxy silanes [D ) R 2 Si(OR′) 2 , T ) RSi(OR′) 3 , Q ) Si(OR′) 4 ] (eq 1). These novel frameworks have desirable and tunable mechanical, chemical, and physical properties such as adjustable porosity, chemical inertness, and a defined swelling capacity of the final polysiloxane matrices.…”

Section: Introductionmentioning

confidence: 99%

“…38 Of particular interest was the fluxional behavior of the nonrigid complex HRuCl-(P∼O) 2 (PkO) containing two monodentate ether-phosphine ligands (P∼O) and one bidendate (PkO) ligand. By VT 31 P{ 1 H} NMR spectroscopic investigations in solution 39,40 and by corresponding 31 P CP MAS NMR measurements in the solid state, it was found that not only the monomeric but also the polymer supported ruthenium complex undergoes a chemical exchange. 1 In the latter case, this happens only in the interphase.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Polysiloxane-Bound (Ether−phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases¹

Lindner¹,

Schreiber²,

Schneller³

et al. 1996

Inorg. Chem.

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The reaction of two equiv of the monomeric ether-phosphine O,P ligand (MeO)(3)Si(CH(2))(3)(Ph)PCH(2)-Do [1a(T(0)()), 1b(T(0)())] {Do = CH(2)OCH(3) [1a(T(0)())], CHCH(2)CH(2)CH(2)O [1b(T(0)())]} with PdCl(2)(COD) yields the monomeric palladium(II) complexes Cl(2)Pd(P approximately O)(2) [2a(T(0)())(2)(), 2b(T(0)())(2)()]. The compounds 2a(T(0)())(2)() and 2b(T(0)())(2)() are sol-gel processed with variable amounts (y) of Si(OEt)(4) (Q(0)()) to give the polysiloxane-bound complexes 2a(T(n)())(2)()(Q(k)())(y)(), 2b(T(n)())(2)()(Q(k)())(y)() (Table 1) {P approximately O = eta(1)-P-coordinated ether-phosphine ligand; for T(n)() and Q(k)(), y = number of condensed T type (three oxygen neighbors), Q type (four oxygen neighbors) silicon atoms; n and k = number of Si-O-Si bonds; n = 0-3; k = 0-4; 2a(T(n)())(2)()(Q(k)())(y)(), 2b(T(n)())(2)()(Q(k)())(y)() = {[M]-SiO(n)()(/2)(OX)(3)(-)(n)()}(2)[SiO(k)()(/2)(OX)(4)(-)(k)()](y)(), [M] = (Cl(2)Pd)(1/2)(Ph)P(CH(2)Do)(CH(2))(3)-, X = H, Me, Et}. The complexes 2b(T(n)())(2)()(Q(k)())(y)() (y = 4, 12, 36) show high activity and selectivity in the hydrogenation of 1-hexyne and tolan. The dicationic complexes [Pd(P&arcraise;O)(2)][SbF(6)](2) [3a(T(0)())(2)(), 3b(T(0)())(2)()] are formed by reacting Cl(2)Pd(P approximately O)(2) with 2 equiv of a silver salt {P&arcraise;O = eta(2)-O&arcraise;P-coordinated ether-phosphine ligand; 3a(T(0)())(2)(), 3b(T(0)())(2)() = [M]-SiOMe(3); [M] = {[Pd(2+)](1/)(2)P(Ph)(CH(2)CH(2)OCH(3))(CH(2))(3)-}{SbF(6)} (a), {[Pd(2+)](1/)(2)P(Ph)(CH(2)CHCH(2)CH(2)CH(2)O)(CH(2))(3)-}{SbF(6)} (b)}. Their polysiloxane-bound congeners 3a(T(n)())(2)(), 3b(T(n)())(2)() {[M]-SiO(n)()(/2)(OX)(3)(-)(n)} are obtained if a volatile, reversible bound ligand like acetonitrile is employed during the sol-gel process. The bis(chelate)palladium(II) complexes 3a(T(n)())(2)(), 3b(T(n)())(2)() are catalytic active in the solvent-free CO-ethene copolymerization, producing polyketones with chain lengths comparable to those obtained with chelating diphosphine ligands. The polysiloxane-bound palladium(0) complexes 5a(T(n)())(2)()(Q(k)())(4)(), 5b(T(n)())(2)()(Q(k)())(4)() {[M]-SiO(n)()(/)(2)(OX)(3)(-)(n)}(2)[SiO(k)()(/2)(OX)(4)(-)(k)](4), [M] = [(dba)Pd](1/)(2)P(Ph)(CH(2)Do)(CH(2))(3)-} undergo an oxidative addition reaction with iodobenzene in an interphase with formation of the complexes PhPd(I)(P approximately O)(2).4SiO(2) [6a(T(n)())(2)()(Q(k)())(4)(), 6b(T(n)())(2)()(Q(k)())(4)()] {[M]-SiO(n)()(/)(2)(OX)(3)(-)(n)](2)[SiO(k)()(/2)(OX)(4)(-)(k)](4), [M] = [PhPd(I)](1/2)P(Ph)(CH(2)Do)(CH(2))(3)-}, which insert carbon monoxide into the palladium-aryl bond even in the solid state.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis of Polysiloxane-Bound (Ether−phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases¹

Lindner¹,

Schreiber²,

Schneller³

et al. 1996

Inorg. Chem.

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Metallkomplexkatalysatoren mit Phosphons�ureester-Phosphan-Liganden. I. Carbonylierung von Methanol mit Phosphons�ureester-Phosphan-Rhodiumkomplexen in der Fl�ssigphase

Freiberg¹,

Weigt²,

Dilcher³

1993

J. Prakt. Chem.

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Metal Complex Catalysts with Phosphonic Ester Phosphine Ligands. I. Carbonylation of Methanol by Phosphonic Ester Phosphine Rhodium Complexes The treatment of technically available 2‐(chloroethyl)phosphonic acid dimethylester (1) with diphenylphosphine and potassium‐tert.‐butylate affords 2‐(diphenylphosphino)ethylphosphonic acid dimethylester (2a) in a simple way. 2a can be used as a hemilabil complex ligand (by phosphine and phosphoryl group.) Rhodium complexes of the type (MeO)2P(O)CH2CH2P(Ph)2RhL3 (3) were obtained from 2a and exhibit excellent catalytic properties in the liquid‐phase carbonylation of methanol to acetic acid. Studies on other chelat‐ligands did not confirm the exceptional increase of the activity by bisphosphinemonoxyd‐ligands and the inhibition of the title reaction by bisphosphine‐ligands already published.

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Alcohols and Derivatives by Homologation with Syngas

Braca

1994

Oxygenates by Homologation or CO Hydrogenation With Metal Complexes

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Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung

Cited by 10 publications

References 31 publications

Synthesis of Polysiloxane-Bound (Ether−phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases¹

Synthesis of Polysiloxane-Bound (Ether−phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases¹

Metallkomplexkatalysatoren mit Phosphons�ureester-Phosphan-Liganden. I. Carbonylierung von Methanol mit Phosphons�ureester-Phosphan-Rhodiumkomplexen in der Fl�ssigphase

Alcohols and Derivatives by Homologation with Syngas

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Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung

Cited by 10 publications

References 31 publications

Synthesis of Polysiloxane-Bound (Ether−phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases1

Synthesis of Polysiloxane-Bound (Ether−phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases1

Metallkomplexkatalysatoren mit Phosphons�ureester-Phosphan-Liganden. I. Carbonylierung von Methanol mit Phosphons�ureester-Phosphan-Rhodiumkomplexen in der Fl�ssigphase

Alcohols and Derivatives by Homologation with Syngas

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Synthesis of Polysiloxane-Bound (Ether−phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases¹

Synthesis of Polysiloxane-Bound (Ether−phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases¹