Issue 9, 2014

Synthesis, properties and structures of NbOF3 complexes and comparisons with NbOCl3 analogues

Abstract

The first series of complexes of niobium(V) oxide trifluoride, [NbOF3(OPR3)2] (R = Me or Ph), [NbOF3(dppmO2)] (dppmO2 = Ph2P(O)CH2P(O)Ph2), [NbOF3(dmso)2], [NbOF3(tmeda)] (tmeda = Me2N(CH2)2NMe2) and [NbOF3(diimine)] (diimine = 2,2′-bipy, 1,10-phen) have been prepared, either by reaction of the corresponding complexes of NbF5 and hexamethyldisiloxane (HMDSO) in CH2Cl2–MeCN solution, or directly from NbF5, ligand and HMDSO. They were characterised by IR, 1H, 31P{1H} and 19F{1H} NMR spectroscopy, and X-ray crystal structures are reported for [NbOF3(OPR3)2] (R = Me or Ph) and [NbOF3(dppmO2)]. Complexes of NbOCl3, [NbOCl3(OPPh3)2], [NbOCl3(dppmO2)], [NbOCl3(dppeO2)] (dppeO2 = Ph2P(O)(CH2)2P(O)Ph2), [NbOCl3(tmeda)] and [NbOCl3(diimine)] were made from NbCl5 and HMDSO in MeCN (which forms [NbOCl3(MeCN)2] in situ), followed by addition of the neutral ligand. Their properties are compared with the oxide fluoride analogues. X-ray structures are reported for [NbOCl3(dppmO2)], [NbOCl3(dppeO2)], [NbOCl3(tmeda)] and [NbOCl3(2,2′-bipy)]. The synthesis and spectroscopic characterisation of [MF5L] (M = Nb or Ta; L = OPR3, OAsPh3) and [MF4(diimine)2][MF6] are also described, and the key properties of the four series of complexes compared.

Graphical abstract: Synthesis, properties and structures of NbOF3 complexes and comparisons with NbOCl3 analogues

Supplementary files

Article information

Article type
Paper
Submitted
25 Nov 2013
Accepted
23 Dec 2013
First published
03 Jan 2014
This article is Open Access
Creative Commons BY license

Dalton Trans., 2014,43, 3649-3659

Synthesis, properties and structures of NbOF3 complexes and comparisons with NbOCl3 analogues

W. Levason, G. Reid, J. Trayer and W. Zhang, Dalton Trans., 2014, 43, 3649 DOI: 10.1039/C3DT53322K

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