15972-91-5Relevant academic research and scientific papers
Development of a 4,4′-biphenyl/phosphine-based COF for the heterogeneous Pd-catalysed telomerisation of 1,3-butadiene
Hausoul, Peter J. C.,Eggenhuisen, Tamara M.,Nand, Deepak,Baldus, Marc,Weckhuysen, Bert M.,Klein Gebbink, Robertus J. M.,Bruijnincx, Pieter C. A.
, p. 2571 - 2579 (2013/09/24)
The improved synthesis, characterisation and application of a microporous 4,4′-biphenyl/phosphine-based covalent organic framework (COF) for the heterogeneous Pd-catalysed telomerisation of 1,3-butadiene with phenol and glycerol are presented. The solid polyphosphine is amorphous, microporous and an excellent support for Pd(acac)2. Solid-state NMR and DRIFT analysis of materials of varying Pd-loading show that bis-phosphine complexes of palladium are preferably formed. Under solvent- and base-free conditions, high conversions and selectivities are obtained for this catalyst material with both phenol and glycerol as substrates. The product selectivity, with both butenylation and telomerisation activity observed with phenol, can be tuned by variation of the metal loading. For glycerol it is shown that the selectivity to the undesired tri telomer is low under all applied conditions and, remarkably, that the heterogeneous catalyst outperforms its homogeneous PPh 3-based counterpart.
A highly efficient catalyst for the telomerization of 1,3-dienes with alcohols: First synthesis of a monocarbenepalladium(0)-olefin complex
Jackstell, Ralf,Andreu, Mario Gomez,Frisch, Anja,Selvakumar, Kumaravel,Zapf, Alexander,Klein, Holger,Spannenberg, Anke,Roettger, Dirk,Briel, Oliver,Karch, Ralf,Beller, Matthias
, p. 986 - 989 (2007/10/03)
Industrial reaction improved: The first monocarbenepalladium(0)-olefin complex has been isolated and characterized (see structure; Pd orange, N green, S yellow, O blue). The complex exhibited unprecedented high catalyst productivity and selectivity for in
Cationic η3-allyl complexes. 21. Telomerization of buta-1,3-diene with Z-H compounds mediated by group 10 complexes
Bouachir, Faouzi,Grenouillet, Pierre,Neibecker, Denis,Poirier, Jacques,Tkatchenko, Igor
, p. 203 - 215 (2007/10/03)
Cationic (η3-allyl) complexes of general formula [(η3-allyl)M(ligand)2]+Y-, where Y- is a non-coordinating anion (BF4-, ClO4-, BF4-) have been examined in telomerization reactions of buta-1,3-diene with representative nucleophiles. No reaction are observed for nickel complexes, due to their high reactivity versus nucleophiles. With palladium complexes, the reaction only occurs with alcohols and provides an increased selectivity for telomers with more than two diene units, leading to C16, C24 and even higher ethers. Although much less reactive, platinum complexes can also produce higher telomers when hydrogenosilanes are used. It is proposed, at least in the case of palladium, that the formation of C16 and C24 ethers arises from the coupling of C8 units within dimeric palladium intermediates with the telogen acting as a bridging ligand.
