Coll(salen)t derivatives whose ethanediyl moiety carries an o-alkenyl side chain react with oxygen and methanol or ethanol t o give, via interaction between intermediate Colll species and the pendant olefin, alkylated products with a P-alkoxy substituted carbon bridge between cobalt and the equatorial ligand; the corresponding intermolecular reaction between Coll(salen) and hex-I-ene does not take place.
The synthesis of Hzsalen (2.2'-[ethane-I ,2-diylbis(nitrilomethylidyne)]diphenol} derived models 1 for coenzyme B,, with a carbon bridge between the ligand and cobalt has been accomplished by condensation of salicylaldehyde and o-substituted 1,2-diamines 8 followed by complexation with Co", reduction to Co' complexes, and intramolecular alkylation. The structures of intramolecularly alkylated Co(salen) complexes with a bridge of three, 1 b, and of four methylene groups, Ic, have been investigated by N M R spectroscopy and determined by X-ray crystallography.
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