Catalytic oligomerisation of butadiene using catalysts derived directly from metal atoms or di(η-arene)titanium compounds

Using Metal Atoms and Molecular High-Temperature Species in New Materials Synthesis

“…(63) This finding is part of a wider study which used the paradigm of Ziegler-Nat ta catalysis to explore VS-based procedures for rapid screening of oligomerization and polymerization catalysts and co-catalysts. (63) High defect MgCl 2 structures suitable as MgCl 2 _ supported ZieglerNatta catalysts can be isolated from cocondensation reactions of MgCl 2 vapors, a co-dispersant and TiCl u . (64) Additional applications of VS to polymer science can be found in a review of the field, (40) where six important areas of synthesis have been identified where VS has contributed.…”

Late Transition Metals, Metal Halides, Metal Oxides, and Metal Sulfides (Group VIII)

“…113 M. L. H. Green and co-workers have briefly investigated the capacity of Fe, Co, and Ni atoms to oligomerize 1,3-butadiene. 114 ' 115 Benzene and diluent were also simultaneously deposited, and presumably arene-Μ complexes are intermediates. Fe formed mainly diene trimers, whereas Co and Ni yielded dimers.…”

“…192 Table 5-11 summarizes available vaporization data in the literature and includes the vapor composition when available. 114,[193][194][195][196][197][198][199][200][201][202][203][204][205][206][207][208][209][210][211][212] Many of the metal halides of this series are quite volatile, but vaporize as telomers. Many of the oxides and sulfides are not thermally stable.…”

Early Transition Metals, Metal Halides, Metal Oxides, and Metal Sulfides Groups IIIB–VIIB)

“…66 M. L. H. Green and co-workers have carried out a wide variety of butadi ene oligomerization experiments using metal atoms or products from metal atom reactions as catalysts. 67 ' 68 A summary of these studies 36,37 indicates that in the presence of benzene [which can complex the metal atoms to yield (C 6 H 6 ) 2 M], Ti yielded polymer with butadiene, V and Cr yielded oligomers plus triene, and Mn yielded trimer. The addition of the alkylating agent Et 2 AlCl caused some product distribution changes, but mainly a great increase in % diene converted.…”

“…Several other catalytic systems were also investigated, including Μ atom-AI atom, Μ atom-AI atom-EtCl, Al atom-TiCl 4 , Μ atom-EtCl, Μ atom-P(C 6 H 5 ) 3 , Ti0 2 , FeO, and NiO. 67,68 Overall, these studies add to the weight of evidence that metal atom vapor synthesis techniques may someday be useful for low-temperature catalysis processes. One possible application would be low-temperature polymeriza tion on surfaces.…”