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 modern, this moment variation is because of the quick development within the box, sparked by way of the invention of various well-defined steel carbene complexes that could act as very effective initiators of every kind 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 easy olefin metathesis.Olefin Metathesis and Metathesis Polymerization presents a vast, up to date account of the topic from its beginnings in 1957 to the newest functions in natural synthesis. The booklet follows an analogous structure because the unique, making it worthy toteachers and to researchers, and may be of specific curiosity to these operating within the fields of natural chemistry, polymer chemistry, organometallic chemistry, catalysis, fabrics technology and chemical engineering.
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Extra resources for Olefin Metathesis and Metathesis Polymerization
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20); (Candlin 1974; Iwasawa 1978). CI C12 Mo ~ AI-O / \CI 0~ (24) /C3H5 ooc ~ (IV)/C3H5 Mo + 2 C3H6 ~ C3H5 ~ AI-O / ~ C3H5 H2 I (20) 600~ \/ A1-O \ (IV) ~/AI-O \ (VI)//O ~ A1-O \ (II) 02 02 Mo ; Mo = 0 ; Mo%0 \/AI-O / 0~ \/AI-O / 300~ ~/AI-O / Mo (21) NN ~/AI-O (22) H2 600oc// (20) (23) compound 20 can be converted into 21-24 by stoichiometric reactions with H2, C12, or 02. 3 Examples of supported molybdenum catalysts for metathesis reactions a Catalyst system T/~ Substrate Reference MoO3/A1203 M003/A1203 MoO3/CoO/A1203 M003/y-A1203/LiA1H4 MoO3/A12Oa/Et3A1 MoO3/AI203/Me3A1 MoO3/A1203/Bu4Sn MoO3/SiO2 MoO3/fl-TiO2 MoO3/fl-TiOz/Me4Sn MoO3/SnOz/Me4Sn MoO3/ZrO2 Mo(CO)6/A1203 Mo(CO)6/MgO Mo(CO)6/SiO2 Mo(CO)6/ZnO/O2 Mo(CO)6/HNa-Y zeolite Mo(CO)6/TiOz Mo(CO)6/carbon (176-C6H6)MO(CO)3/A1203 MoCIJNa-mordenite Mo(NMe/)4/SiO2 Mo2(NMe2)6/SiO2 MOE(OAc)4/A1203b Mo2(OAc)4/SiO2 20-180 40 150 20 20-100 60 Pent-2-ene Propene Propene Cycloalkenes Propene Non- 1-ene Hept-l-ene Propene Propene-d6 + do Propene-d6 + do Propene Propene Propene Propene Propene Propene Propene Propene Propene Propene Propene Ethene~ Ethenec Propene Propene Propene, etc.
A number of stable [Mt]=CHCMe3 complexes (Mt=Nb, Ta) have been prepared which react with terminal olefins in various ways depending on the nature of the ligands. 3. Survey of Catalyst Systems Me3CCH--Ta(C1)2Cp 23 Me3CCH--[Ta] + ; I CH2-CH2 Me3CCH2 + I -~ [Ta] I CH2-- CH2 CH=CH2 (18) Note that there is a preferred direction of reaction with the original complex. 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.
Tungsten(VI) carbyne complexes exhibit varying degrees of metathesis activity, depending on the ligands. For instance, W(-CCMe3)(C1)3(dme) catalyzes the metathesis of linear and cyclic olefins at 20~ (Weiss 1986a, 1988c), whereas W(-CCMe3)(OCMe3)3 only becomes active for the metathesis of oct-l-ene in hexane at 69~ after reaction with SiO2. The carbyne complex is presumed to react with the weakly Br6nsted-acidic Si-OH protons, resulting in a Schrock-type tungsten carbene complex (Weiss 1989b,c); reaction (23).