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Original Articles

CYCLORHODATION OF (1-PYRROLIDINOTHIOCARBONYL)-AROMATICS

Pages 137-145 | Received 14 Aug 1998, Published online: 22 Sep 2006
 

Abstract

Pyrrolidinothiocarbonyl groups promote cyclorhodation of an aromatic ring with [RhCl3(PBu3)2] (PBu3 = tri-n-butylphosphine): thus p-(l-pyrrolidinothiocarbonyl)toluene (Htpr). 2-(l-pyrroli-dinothiocarbonyl)naphthalene (Hbnr), 2-(l-pyrrolidinothiocarbonyl)benzo[b]thiophene (Htnp) and l,3-bis(l-pyrrolidinothiocarbonyl)benzene (Hmpr) gave, respectively, [RhCl2(tpr)(PBu3)2], [RhCl2(bnr)(PBu3)2], [RhCl2(tnp)(PBu3)2], and [RhCl2(mpr)(PBu3)2]. These complexes were characterized spectroscopically. The two PBu3 ligands are trans to each other and the thioamides behave as uninegative, bidentate C-S donors. Htpr was rhodated at the ortho position, Hbnr at position 3, Htnp at position 3, and Hmpr at position 4 against the expected position 2 in which case it could act as an S-C-S terdentate ligand. Reactions of Htpr, Htnp, and Hbnr with RhCl3(H2O)3 gave no definite cyclorhodated product but Hmpr afforded [RhCl2(mpr)(H20)] where mpr was cyclorhodated at position 2 and chelated as an S-C-S terdentate ligand.

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