Effects of transition metals on hydrogen transfer and exchange in catalytic oligomerization of butadiene

✍ Scribed by Sei Otsuka; K. Taketomi

• Publisher: Elsevier Science
• Year: 1966
• Tongue: English
• Weight: 511 KB
• Volume: 2
• Category: Article
• ISSN: 0014-3057
• DOI: 10.1016/0014-3057(66)90049-8

✦ Synopsis

Linear oligomerization of three deuterium isomers of butadiene (C4H6, C4H2D4, C,D6) was effected by C02(CO)s-A1Eta (I) and C0(C3H5)3, and cyclo-oligomerization of C4H6 by Ni(CO)4-AIEt3 (II) and Ni(C3Hs)2. Isotopic isomers of 3-methyl-l,4,6-heptatriene(MHT) were obtained; NMR studies indicated that only 1,4-hydrogens of butadiene migrate to form MHT and participate in hydrogen exchange between monomers. The hydrogen exchange rate was significant under the influence of (I), but negligible in the case of (II) as shown by mass spectroscopy of the deuterated butadienes recovered. Effectiveness of a transition metal for the hydrogen exchange appears to be a major factor in determining the reaction path.

Oligomerization of BD-d4 and BD-d6 by Coz(CO)s-AIEt3.

An apparatus for preparation of isotopic isomers of MHT is shown in Fig. . A typical procedure is as follows: BD was dried in C with molecular sieve 4A. After the atmosphere of A was replaced with