Issue 36, 2013

Coordination complexes of NbX5 (X = F, Cl) with (N,O)- and (O,O)-donor ligands and the first X-ray characterization of a neutral NbF5 adduct

Abstract

A variety of fairly air-stable complexes were prepared by straightforward reactions of NbX5 (X = F, Cl) with a series of potential bidentate (N,O)- and (O,O)-donor ligands in CH2Cl2. NbF5 reacted with equimolar amounts of 2-[(2,6-diisopropylphenyl)iminomethyl]phenol (dpimpH) and 2-benzoyl-6-hydroxy-6-phenylpentafulvene (bhpfH) to afford the mononuclear complexes NbF51(O)-OC6H4CH[double bond, length as m-dash]NHC6H3(CHMe2)2], 2, and NbF51(O)-bhpfH], 7, respectively. The 1 : 1 reactions of NbF5 with salicylaldehyde oxime (saoH2) and 2-phenylaminoethanol gave the hexafluoroniobato salts [NbF41(O)-ON(H)[double bond, length as m-dash]CHC6H4OH}2][NbF6], 3, and [NbF41(O)-OCH2CH2NH2Ph}2][NbF6], 6, respectively. The syntheses of 2, 3 and 6 are accompanied by oxygen to nitrogen intramolecular H migration, leading to the formation of metal–alkoxide moieties. The parallel chemistry of NbCl5 is characterised by HCl release. The 1 : 1 reactions with dpimpH, saoH2 and bhpfH yielded, respectively, the ionic complex [NbCl21(N):κ1(O)-dpimp}2][NbCl6], 4a, the neutral-dinuclear Nb2Cl71(O)-saoH][κ2(O)-sao], 5, and the mononuclear NbCl42(O)-bhpf], 8. The tantalum species [TaCl21(N):κ1(O)-dpimp}2][TaCl6], 4b, was prepared from TaCl5/dpimpH. The new products 2–8 were fully characterized by analytical and spectroscopic techniques. Moreover the solid state structures of 2 and 8 were ascertained by X-ray diffraction studies; the structure of 2 exhibits an intramolecular bifurcated N–H⋯(O,F) hydrogen bond. DFT calculations were carried out in order to predict the lowest energy structures in the distinct cases, showing generally good agreement with the experimental data.

Graphical abstract: Coordination complexes of NbX5 (X = F, Cl) with (N,O)- and (O,O)-donor ligands and the first X-ray characterization of a neutral NbF5 adduct

Supplementary files

Article information

Article type
Paper
Submitted
08 Apr 2013
Accepted
04 Jul 2013
First published
22 Jul 2013

Dalton Trans., 2013,42, 13054-13064

Coordination complexes of NbX5 (X = F, Cl) with (N,O)- and (O,O)-donor ligands and the first X-ray characterization of a neutral NbF5 adduct

M. Bortoluzzi, F. Marchetti, G. Pampaloni, M. Pucino and S. Zacchini, Dalton Trans., 2013, 42, 13054 DOI: 10.1039/C3DT50930C

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