By K. J. Ivin, J. C. Mol

This e-book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the traditional textual content within the box brand new, this moment variation is end result of the swift development within the box, sparked by way of the invention of diverse well-defined steel carbene complexes that could act as very effective initiators of all kinds of olefin metathesis response, together with ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, in addition to uncomplicated olefin metathesis.Olefin Metathesis and Metathesis Polymerization presents a extensive, up to date account of the topic from its beginnings in 1957 to the most recent purposes in natural synthesis. The booklet follows an identical layout because the unique, making it worthy toteachers and to researchers, and should be of specific curiosity to these operating within the fields of natural chemistry, polymer chemistry, organometallic chemistry, catalysis, fabrics technological know-how and chemical engineering.

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Additional info for Olefin Metathesis and Metathesis Polymerization

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A X is MeCCI(OH)(CH2C1). e MeCN improves selectivity (94%). f OAr-various substituted phenoxides, g AXn--ZrC14, AICl3, TIC14. h Electrolysis in a halogenated solvent; high selectivity (95-100%). ix - 2, 4. j The most active is WCI4(OC6H3-X2-2,6)2 (X = C1, Br). k Mt = Sn, Pb; R - Me, Bu; order of activity for a given cocatalyst: X = Me < Ph < F < C1 < Br; for a given precursor complex, the activity increases in the order Me4Sn < Bu4Sn < Bu4Pb. 1]hept-2-ene. n Cis content of polymer shows strong dependence on temperature: 100% and 10% at -50~ and 30~ respectively, p y-- 1-3.

The reaction is prevented from developing into a chain reaction by the propensity of the [Ta]=CH2 complex to undergo the homologation reaction (McLain 1977; Schrock 1980; Rocklage 1981); see Abbenhuis (1994) for another example of a tantalum carbene complex which will undergo only stoichiometric metathesis. 2) are good initiators of ROMP as also is the tantalacyclobutane complex derived from 2 by the addition of norbornene. The complexes 1 and 2 are both effective for the metathesis of cis-pent-2-ene.

1972 Chatt 1972 Moulijn 1971 Rybak 1987 Rybak 1987 Farona 1975 20 20 20 Pent- 1-ene Pent-2-ene Pent-2-ene Kroll 1972 Kittleman 1970 Kittleman 1970 50-100 Hept-3-ene Warwel 1983b ReEO7/A1203/MtxOyc Re207/A12Oa/Bu4Sn Re207/A12Oa/R4Sn ReEO7/A12Oa/Et4Pb ReEO7/A1203/MoO3/Bu4Sn Re2OT/SiO2-A1203 Re2OT/SiO2-A1203/R4Sn Re2OT/SiO2-AlzO3/Et3A1 Re2OT/TiO2/Et3A1/MeaSn Re203/unsupported and on SiO2 CH3ReO3/SiO2-A1203 CH3ReO3/Nb205 CH3ReO3/R,,A1C13_,, (ArO)2AI(THF)[OAI(OAr)(THF)] OReO3d ReC15 ReC15/EtAICI2 ReCls/Et3A1/O2e ReCIs/LiAIH4f ReC15/Bu4Sn ReOC13(PPh3)2/EtA1C12 ReOC13[P(OEt)3]2/EtA1C12 Re(CO)sX/EtA1C12g Na[(CO)sMt-Re~CO)5]/ MeA1C12/R4NCI" ReC14(PPh3)/EtA1C12 ReBr3(O)(PPh3) Ph2Ge-Re (CO)4(COMe) / i-BuAIC12 20-100 20 20 35 20 25-50 25 20 40 2 00 20 20 20 a Other supports tried include SiO2 (Aldag 1977; Edreva-Kardjieva 1986), SnO (Bradshaw 1968) and MgO (Edreva-Kardjieva 1977).

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