- Polyethylene-Bound Rhodium(I) Hydrogenation Catalysts
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Homogeneous, recoverable hydrogenation catalysts were prepared with use of functionalized ethylene oligomers as ligands.Phosphine groups were introduced onto ethylene oligomers following anionic oligomerization of ethylene.The product polyethylenediphenyl
- Bergbreiter, David E.,Chandran, Rama
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- Reversible mechanochemistry of a PdII coordination polymer
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Breaking up and making up: The ultrasonic cleavage of high-molecular-weight linear coordination polymers of phosphane telechelic polytetrahydrofuran and palladium dichloride in dilute solution is a reversible process (see picture). Sonication for 1 h led
- Paulusse, Jos M. J.,Sijbesma, Rint P.
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- Quantification of ultrasound-induced chain scission in Pd II-phosphine coordination polymers
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A kinetically inert, reversible coordination polymer (3) was obtained through complexation of dicyclohexylphosphine telechelic poly(tetrahydrofuran) with palladium(II) dichloride. This coordination polymer is unreactive towards palladium(II) dichloride bis(1-diphenylphosphino)dodecane (4), because ligand dissociation in the coordination polymer is slow. However, upon ultrasonication of solutions of 3 in toluene in the presence of 4, formation of palladium(II) heterocomplexes was observed with 31P NMR spectroscopy. Heterocomplex formation, the consumption of 4, and changes in molecular weight were used to quantify the scission process. In the presence of 60 equivalents of the alkyldiphenylphosphine stopper complex, the reduc-tion in molecular weight was strongly enhanced ; over a period of eight hours the weight-averaged molecular weight was reduced from 1.1×105 to 2.3 × 104 g mol-1 while 47% of the palladium(II) complexes in the coordination polymer had been converted into heterocomplexes. These results show that the system of 3 in combination with scavenger 4 is a suitable system to study the efficiency of ultrasound-induced chain scission of coordination polymers.
- Paulusse, Jos M. J.,Huijbers, Jeroen P. J.,Sijbesma, Rint P.
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- A high molecular weight reversible coordination polymer of PdCl2 and 1,12-bis(diphenylphosphino)dodecane
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1,12-Bis(diphenylphosphino)dodecane and PdCl2 are shown to form linear supramolecular polymers in equilibrium with cyclic structures; high molecular weight material was obtained by melt polymerisation.
- Paulusse, Jos M. J.,Sijbesma, Rint P.
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- Palladium-catalyzed C(sp3)–P(III) bond formation reaction with acylphosphines as phosphorus source
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Palladium-catalyzed C(sp3)–P(III) bond formation reaction for alkyl substituted phosphines preparation was developed. In this reaction, various alkyl bromides and limited alkyl chlorides reacted with acylphosphine under relative mild and easily accessible condition, and differential phosphines were afforded in good yields. This reaction made up the application of palladium catalysis in C(sp3)–P(III) bond formation, and indicated a practical application of acylphosphine as a phosphination reagent.
- Zhang, Mengyue,Ma, Zhichao,Du, Hongguang,Wang, Zhiqian
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- Alkyl diphenyl phosphine and preparing alkyl diphenyl phosphine payment proportional to production alkyl benzene
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The invention discloses alkyl diphenylphosphine and a method for preparing alkyl diphenylphosphine with co-production of alkylbenzene. The structural formula of alkyl diphenylphosphine is shown in a formula I. The method comprises: adding triphenylphosphine and metal lithium into an organic solvent for reaction for 3-6 hours at room temperature; and cooling the reaction system to 0-10 DEG C, adding halogenated straight-chain alkane for insulating reaction, then raising the temperature of the system to 30-80 DEG C, keeping the temperature to react for 1-3 hours, removing the organic solvent and reducing the pressure and distilling to separately obtain alkyl diphenylphosphine and alkylbenzene. According to the alkyl diphenylphosphine disclosed by the invention, alkyl is directly bonded with P, so that the alkyl diphenylphosphine can be dissolved in most solvents and can be used as a ligand for homogeneous catalysts. By virtue of the method disclosed by the invention, high value straight-chain alkylbenzene is co-produced while straight-chain alkyl diphenylphosphine is prepared by way of a one-pot process. Use of chloro-tert-butane which is relatively high in price and waste of the metal lithium are avoided. The method is simple to operate, efficient, low in energy consumption, low in cost and suitable for large-scaled industrial production.
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Paragraph 0074; 0078-0081
(2017/08/25)
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- Photoinduced Coupling Reaction of Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide with Interelement Compounds: Application to the Synthesis of Thio- or Selenophosphinates
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Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TMDPO) is a radical initiator widely used in the field of macromolecular chemistry, but not often applied in synthetic organic chemistry. We have focused on the use of TMDPO as a phosphorus source in reactions with different E - E compounds, where E - E represents a heteroatom-heteroatom bond, under photoirradiation. Interestingly, the cross-coupling reaction between TMDPO and disulfides or diselenides successfully affords thio- or selenophosphinates and thio- or selenoesters, respectively. The synthesis of series of thio- and selenophosphinates by this photoinduced cross-coupling reaction is demonstrated.
- Sato, Yuki,Kawaguchi, Shin-Ichi,Nomoto, Akihiro,Ogawa, Akiya
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p. 3558 - 3567
(2017/08/16)
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- Selectivity of mechanochemical chain scission in mixed palladium(II) and platinum(II) coordination polymers
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The selectivity of ultrasound induced chain scission was studied in reversible polymers with coordinative bonds (Pd-P and Pt-P) of different strengths in series. The Royal Society of Chemistry.
- Paulusse, Jos M. J.,Sijbesma, Rint P.
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supporting information; experimental part
p. 4416 - 4418
(2009/05/06)
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- Reversible, high molecular weight palladium and platinum coordination polymers based on phosphorus ligands
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A general strategy for the preparation and characterization of high molecular weight coordination polymers based on bifunctional phosphorus ligands and palladium or platinum dichloride is described. Metal-to-ligand stoichiometry is of key importance for t
- Paulusse, Jos M. J.,Huijbers, Jeroen P. J.,Sijbesma, Rint P.
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p. 6290 - 6298
(2008/02/02)
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