Two silver–containing polyoxometalate–based inorganic–organic hybrids as heterogeneous bifunctional catalysts for construction of C–C bonds and decontamination of sulfur mustard simulant.

The construction of C–C bonds and degradation of chemical warfare agents (CWAs) are two central organic conversions for future sustainable development. Herein, two remarkable silver-containing polyoxomolybdates-based hybrids (Ag-POMos), [Ag(L)(H 2 O) 2 ] 2 [HPMo 12 O 40 ] (1) and [Ag 2 (L) 2 ] 2 [HPMo 10 V 2 O 40 ]·4DMSO (2) (L ​= ​4,6-bis(2-pyridyl)-2-aminopyrimidine) were designed and prepared by using silver cation, polyoxomolybdates and multiple N-donors ligand (L). The structure of compound 1 is constructed from an independent Ag center and a keggin-type POMs; compound 2 is composed of two independent Ag centers and a keggin-type POMs, which displays intriguing POM-incorporated 1-D chain structure with hydrogen bonding. Additionally, Ag-POMos catalysts can be severed as the efficient bifunctional catalysts for the three-component Mannich reaction to achieve the construction of C–C bonds and decontamination of sulfur mustard 2-chloroethyl ethyl sulfide (CEES). As bifunctional heterogeneous catalyst, particularly compound 2 , exhibits satisfying catalytic performances in the Mannich reaction (conv. 99%; sele. 99%) and the oxidation of CEES (conv. 96%; sele. 96%). Notedly, after three runs, compound 2 maintains excellent catalytic properties, demonstrating its remarkable cycling stability. 1. Two novel inorganic-organic silver-polyoxomolybdates hybrids were synthesized for the first time and routinely characterized.2. The compounds can be severed as efficient bifunctional catalysts (functions of Lewis acid catalysis and oxidation catalysis) for the construction of the C–C bond and decontamination of sulfur mustard 2-chloroethyl ethyl sulfide (CEES).3. The molecular compound 2 has good cycling stability, after three continuous runs, the conversion and selectivity have no obvious decrease. [Display omitted] • Designed and synthesis of four- and five-coordinate silver-polyoxomolybdate clusters with bifunctional catalytic properties. • These bifunctional catalysts can efficiently catalyze both Mannich reaction and degradation of sulfur mustard simulant under mild conditions. • The bifunctional catalysts have wide substrate applicability and good catalytic performance. [ABSTRACT FROM AUTHOR]