Applied crystallography by Henryk Morawiec; Danuta Stróż

By Henryk Morawiec; Danuta Stróż

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Addition of alkoxides to [ R ~ ( C - ? Complexes containing O C M C ( C F ~or ) ~ OAr ligands are not stable in the solid state, but are stable in solution, a fact that is consistent with bimolecular decomposition. The complex Re(C-t-Bu)(CH-t-Bu)[OCMe(CFi)2]2 is an active catalyst for metathesis of internal olefins, including methyl oleate, new alkylidene complexes being observed in each case. This appears to be the first documented example of olefin metathesis by a well-characterized rhenium alkylidene complex.

CFz,]Z. W(CH-r-Bu)(NAr)(OR), c2H4 * excess CH,=CH-r-Bu NAr R o 7 4 r t - B u RO (69) OR = OCMe2(CF3),0-r-Bu, OAr the nitrogen atom of the imido ligand occupies the apical position and the two alkoxide oxygens and the two &-carbon atoms of the metallacycle define the basal plane. 58 above the least squares plane defined by these four atoms. The bond angles in this ring are quite different from those in the trigonal bipyramidal metallacycles discussed above. For example, C,-W-C, is only 63" compared to -82" in the two trigonal bipyramidal tungsten complexes.

Thus, A gives the cis product and B gives the trans product. Cyclopropanes are also produced upon photolysis of titanacyclobutane complexes (66). When photolysis is carried out in the presence of disubstituted acetylenes, titanacyclopentadienes are produced. When ethylene is used as the trapping agent, the titanacyclopentane complex is produced. Photolysis in the presence of PMe3 gives the bis(phosphine) adduct C P ~ T ~ ( P MThis ~ ~ )reaction ~. is proposed to proceed via an intermediate metal-centered 1 ,Cbiradical formed by homolytic cleavage of one Ti-C bond.

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