Rhenium and molybdenum oxo-complexes containing ligands related to N-hydroxyiminodipropionic acid

Abstract

The reaction of N-hydroxy-2,2′-iminodipropionic acid with [PPh₄][ReOBr₄], [ReOCl₃(PPh₃)₂], [ReOCl₂(OEt)(PPh₃)₂] or [PPh₄][MoOCl₄(H₂O)] has produced four novel complexes: [ReOBr₃(C₆H₈NO₅)] ^-, [ReOBr₃(C₃H₃NO₂)] ^-, [ReOCl₂(R,S-idpa)]^- (H₃idpa = 2,2′-iminodipropionic acid) and [MoO₂Cl₂(C₃H₄NO₃ )]^-. All have been successfully crystallised as their [PPh₄]⁺ salts which have been characterised by single-crystal X-ray diffraction. The anions [ReOBr₃(C₆H₈NO₅)] ^- and [ReOBr₃(C₃H₃NO₂)] ^- involve tetragonally distorted octahedral Re^VOBr₃ (N,O) centres with the bromides cis to the oxo-group; [ReOCl₂(R,S-idpa)]^- involves a tetragonally distorted octahedral Re^VOCl₂ (O,N,O) centre with the 2Cl cis and O trans to the oxo-group; [MoO₂Cl₂(C₃H₄NO₃ )]^- involves a skew-trapezoidal Mo^VIO₂Cl₂ (N,O) centre with essentially mutual cis oxo-groups and trans chloro-groups. The dimensions of each of these co-ordination spheres are generally typical of related complexes; however, [ReOBr₃(C₃H₃NO₂)] ^- involves an unusually short Re–O_oxo bond of 1.45(4) Å. The organic moieties are considered to arise from rearrangement and/or fragmentation of N-hydroxy-2,2′-iminodipropionic acid, presumably under the influence of the metal centre.

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