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New Silica‐Immobilized Nickel Catalysts for Cyclotrimerizations of Acetylenes
Author(s) -
Reinhard S.,
Šoba P.,
Rominger F.,
Blümel J.
Publication year - 2003
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200202206
Subject(s) - chemistry , catalysis , phosphine , phenylacetylene , cyclooctane , homogeneous catalysis , substrate (aquarium) , turnover number , heterogeneous catalysis , nickel , denticity , solvent , organic chemistry , metal , oceanography , geology
New dicarbonylnickel catalysts with a variety of mono‐ and bidentate phosphine ligands, such as Ph 2 P(CH 2 ) x PPh(CH 2 ) y Si(OEt) 3 (x=2, 3; y=2, 3), have been synthesized and fully characterized, three of them by X‐ray analyses. All the catalysts have been immobilized on silica by reaction of the ethoxysilane or hydroxy groups of the phosphine linkers with the surface silanol groups. The clean immobilization was proved by 31 P solid‐state NMR. It has been demonstrated that the COSi bridge, in contrast to the strong SiOSi bond, is easily cleaved by organic solvents and water. With respect to the cyclotrimerization of phenylacetylene the optimal reaction conditions for all molecular and immobilized catalysts have been determined. Cyclooctane was the best solvent, and the optimal reaction temperature was 100 °C for reactions in homogeneous phase, and 155 °C for surface‐bound catalysts. The bite angles and spacer lengths of the chelating ligands did not play a major role for the performance of the homogeneous or immobilized catalysts. The latter could be recycled for 12 times, with final substrate conversions still typically between 30 and 40%, and turnover numbers (TON) around 1500. With an excess of substrate in one run a TON of 4810 was obtained for an immobilized carbonylnickel complex with a dppp‐type chelate phosphine (x=3, y=2). Reduction of the surface coverage generally resulted in catalysts with longer lifetimes, for example, reduction to one fourth gave a record TON of 7616 for this catalyst. The selectivities of the catalysts all followed one trend. The main products were the cyclotrimers 1,2,4‐ and 1,3,5‐triphenylbenzene, besides dimers, linear trimers and tetramers as side‐products. The fraction of the latter decreased at higher temperatures with homogeneous catalysts, and vanished entirely after a few cycles with the immobilized catalysts. On recycling, the initial ratio of unsymmetrical to symmetrical cyclotrimers of typically 5 : 1 gradually changed to about 1 : 1 for all catalysts.