Re(V) complexes with amino acids based on the '3+2' approach

Five cationic complexes containing the [Re(V)O](3+) core have been prepared by substitution on the precursor [ReIO2(PPh3)(2)]. Complexes with general formula [ReO(dien-H)(aa)](+) have been obtained by reaction of the precurso r with 1 equiv. of dien (diethylenetriamine) and one equivalent of an amino acid (glycine, alanine, valine, leucine, proline). Complexes have been cha racterized by W-Vis and IR spectrophotometry, elemental analyses, H-1 NMR s pectra, HPLC and conductivity measurements. The molecular structures of [Re O(dien-H)(leu)]I.0.5H(2)O and [ReO(dien-H)(pro)]ReO4 have been determined b y means of single-crystal X-ray analyses. Cations consist of a six-coordina ted rhenium atom bonded to two trans-ore groups, one of the [ReO](3+) core and one from the carboxilate. Four nitrogen atoms make the equatorial plane . Three N belong to the dien ligand and the other one to the amino acid. On e of the secondary amine proton of the dien ligand is lost upon coordinatio n. This arrangement corresponds to the so-called '3 + 2' chelating framewor k, with the novel NNN/NO atom set. Complexes are not very stable in aqueous solution. However, solutions in MeOH and DMSO are stable enough to be stud ied by several techniques. The solid state structure seems to be retained i n solution. (C) 2000 Elsevier Science S.A. All rights reserved.