Abstract
The title transformations are oxygen atom transfer, twin isomerization and regiospecific imine oxidation. Bispyridyldiazole ligands have furnished new oxygen atom transfer reagents of coordination type Re V OCl3(NN) which undergo a slower transfer to PPh3 than the corresponding azole reagents. The rate of twin iso - merization (linkage and geometrical) of meridional azole complexes of coordination type Re III (OPnP)Cl3(NN) to facial Re III (PnPO)Cl3(NN) decreases rapidly as n increases in the interval 1-4 (PnP is Ph2P(CH2)nPPh2). An α-diimine chelate of type Re V (NPh)Cl3(NN) is shown to undergo facile oxidation to the corresponding iminoamide complex Re VI (NPh)Cl3(NN) upon treating with dilute nitric acid. The reaction proceeds via regiospecific nucleophilic addition of water to the more polari - zed imine function.
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