Issue 8, 2005

Reactions of a {Mo16}-type polyoxometalate cluster with electrophiles: a synthetic, theoretical and magnetic investigation

Abstract

A medium-nuclearity mixed-valence polyoxomolybdate [H2Mo16O52]10− = {Mo16} (1a) was synthesized using an approach that employed protonated hexamethylenetetramine (HMTAH+) as counter ion and yielded (HMTAH)101a·34 H2O (1). The {Mo16} cluster anion exhibits significant nucleophilicity and traps electrophiles such as divalent transition metal ions, resulting in a family of isostructural compounds based on {Mo16M2}-type anions [M(H2O)8H2Mo16O52]6− (M = FeII (2), MnII (3), CoII (4)). The highly reactive nature of the {Mo16} system is also revealed by rearrangement and decomposition reactions of 1 to either slowly form a sodium-bridged heptamolybdate-based chain compound (5) when left in the reaction solution or, in the presence of very high concentrations of electrophiles, to heptamolybdate-based cluster compounds [M2(H2O)9Mo7O24]2− of the {M2Mo7}-type (M = FeII (6), MnII (7)). Compounds 1–7 were characterised by single crystal X-ray diffraction, elemental analysis, IR spectroscopy, magnetic susceptibility measurements, and density functional theory calculations.

Graphical abstract: Reactions of a {Mo16}-type polyoxometalate cluster with electrophiles: a synthetic, theoretical and magnetic investigation

Supplementary files

Article information

Article type
Paper
Submitted
05 Jan 2005
Accepted
02 Feb 2005
First published
17 Mar 2005

Dalton Trans., 2005, 1372-1380

Reactions of a {Mo16}-type polyoxometalate cluster with electrophiles: a synthetic, theoretical and magnetic investigation

D. Long, P. Kögerler, L. J. Farrugia and L. Cronin, Dalton Trans., 2005, 1372 DOI: 10.1039/B419301F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements