Nucleophilic substitution reaction for rational post-functionalization of polyoxometalates

Abstract

Substitution reactions of polyoxometalate–organic hybrid materials provide a post-functionalization protocol to bring in various additional functional groups.

A Simple Nucleophilic Substitution as a Versatile Postfunctionalization Method for the Coupling of Nucleophiles to an Anderson-Type Polyoxometalate

“…16 In a recent publication of the group of Wei, the authors describe an interesting use of a nucleophilic substitution reaction with a chloride functionalized hybrid hexamolybdate. 17 However, the extent of the reaction was limited to a simple halogen exchange reaction, by reacting the hybrid POM with sodium iodide in acetone, and the substitution of the chloride atom by a nitro group by the reaction with silver nitrate in acetonitrile.…”

“…Nevertheless, over the past 10 years, many postfunctionalization routes have been developed capable of conserving the fragile POM scaffold, while attaching various organic groups to their structure. , These methods include amidation, , esterification, thioesterification, imine bond formation, ,, a Sonogashiro reaction, ,, a Heck reaction, copper catalyzed cycloadditions, − , a Diels–Alder reaction, and finally an N-alkylation . In a recent publication of the group of Wei, the authors describe an interesting use of a nucleophilic substitution reaction with a chloride functionalized hybrid hexamolybdate . However, the extent of the reaction was limited to a simple halogen exchange reaction, by reacting the hybrid POM with sodium iodide in acetone, and the substitution of the chloride atom by a nitro group by the reaction with silver nitrate in acetonitrile.…”

Using Coordination Chemistry to Control “Click” Reactions: The Selective Formation of Asymmetrically Ligated Polyoxometalates

“…(A–E) Survey of monofunctionalized and asymmetric Anderson-Evans-type and Lindqvist-type POMs published in the literature. − (F) Synthesis of symmetric and asymmetric “click” products based on the Lindqvist-type hexavanadate structure (this work).…”

“…In the series of plenary POMs with an octahedral metal–oxo core, monofunctionalized structures can be obtained upon N-ligation of hexamolybdates − (Figure B) as well as in cases of tris ligated mixed-valence vanadium alkoxide clusters, − (Figure D) and rare mixed-metal mono- tris ligated (V 3 Mo 3 ) oxoclusters (Figure C). Topologically appealing monoderived bis-functionalized asymmetric hexavanadate platforms (i.e., molecules suitable for further synthesis of asymmetric hybrids) can, in principle, be obtained as statistically prevalent species by using a huge excess of reactive symmetric POM hybrids to the functionalizing reagent.…”