Redistribution and fluxionality in heteropolyoxoperoxo complexes: [PO4[M2O2(mu-O2)2(O2)2]2]3- with M = Mo and/or W.

Dalton Trans

Systèmes Interfaciaux à l' Echelle Nanométrique, Université Pierre et Marie Curie/CNRS, case 196, 4 place Jussieu, F-75252 Paris cedex 05, France.

Published: March 2004

When peroxotetramolybdophosphate, [(n-C4H9)4N]3[PO4[Mo2O2(mu-O2)2(O2)2]2], denoted (NBu4)3PMo4, and its tungsten(VI) analogue, (NBu4)3PW4, are mixed in acetonitrile at room temperature, redistribution occurs with the formation of three mixed-addenda species [PO4[Mo4-xWxO20]]3- (x = 1-3). The temperature dependence of the phosphorus-31 NMR spectra of a 1 1 mixture and of the pure salts, (NBu4)3PMo4 or (NBu4)3PW4, shows that [MO(O2)2] species are in chemical exchange, as are the [MOp] units of certain heteropolyacids (e.g. H3[PMo12O40] x aq and H3[PW12O40] x aq). However, there is no chemical exchange between free phosphate and [MO(O2)2] species in these systems; but there is fluxional behaviour involving PMo2W2, PMo4 and PW4. This is attributed to the rapid equilibrium between isomers (PMo2W2) and to equilibrium between anionic structures with tridentate (mu-eta2:eta1-O22-) and bidentate (eta2-O22-) modes of coordination for the two peroxo groups of the [M2O2(mu-O2)2(O2)2] moieties.

Download full-text PDF

Source
http://dx.doi.org/10.1039/b315879aDOI Listing

Publication Analysis

Top Keywords

[moo22] species
8
chemical exchange
8
redistribution fluxionality
4
fluxionality heteropolyoxoperoxo
4
heteropolyoxoperoxo complexes
4
complexes [po4[m2o2mu-o22o22]2]3-
4
[po4[m2o2mu-o22o22]2]3- and/or
4
and/or peroxotetramolybdophosphate
4
peroxotetramolybdophosphate [n-c4h94n]3[po4[mo2o2mu-o22o22]2]
4
[n-c4h94n]3[po4[mo2o2mu-o22o22]2] denoted
4

Similar Publications

Redistribution and fluxionality in heteropolyoxoperoxo complexes: [PO4[M2O2(mu-O2)2(O2)2]2]3- with M = Mo and/or W.

Dalton Trans

March 2004

Systèmes Interfaciaux à l' Echelle Nanométrique, Université Pierre et Marie Curie/CNRS, case 196, 4 place Jussieu, F-75252 Paris cedex 05, France.

When peroxotetramolybdophosphate, [(n-C4H9)4N]3[PO4[Mo2O2(mu-O2)2(O2)2]2], denoted (NBu4)3PMo4, and its tungsten(VI) analogue, (NBu4)3PW4, are mixed in acetonitrile at room temperature, redistribution occurs with the formation of three mixed-addenda species [PO4[Mo4-xWxO20]]3- (x = 1-3). The temperature dependence of the phosphorus-31 NMR spectra of a 1 1 mixture and of the pure salts, (NBu4)3PMo4 or (NBu4)3PW4, shows that [MO(O2)2] species are in chemical exchange, as are the [MOp] units of certain heteropolyacids (e.g.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!