A triad of rhenium-mediated transformations |
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| Authors: | Jaydip Gangopadhyay Samir Das Suman Sengupta Indranil Chakraborty and Animesh Chakravorty |
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| Institution: | (1) Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 700 032 Kolkata, India;(2) Jawaharlal Nehru Centre for Advanced Scientific Research, 560 064 Bangalore, India |
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| 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 ReVOCl3(NN) which undergo a slower transfer to PPh3 than the corresponding azole reagents. The rate of twin isomerization (linkage and geometrical) of meridional azole complexes
of coordination type ReIII(OPnP)Cl3(NN) to facial ReIII(PnPO)Cl3(NN) decreases rapidly asn increases in the interval 1–4 (PnP is Ph2P(CH2)nPPh2). An α-diimine chelate of type ReV(NPh)Cl3(NN) is shown to undergo facile oxidation to the corresponding iminoamide complex ReVI(NPh)Cl3(NN) upon treating with dilute nitric acid. The reaction proceeds via regiospecific nucleophilic addition of waterto the more
polarized imine function.
Dedicated to Professor C N R Rao on his 70th birthday |
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| Keywords: | Rhenium-mediated transformations oxygen atom transfer linkage-cum-geometrical isomerization regiospecific imine oxidation |
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