The Counter Cation Effect in the Synthesis and SubsequentReactivity of Polyoxometalates Open Access

Yates, Cindee Keiko (2008)

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This thesis describes the role of counter cations in the synthesis of polyoxometalates. Chapter one describes the role of a cesium ion and how its concentration can afford two structurally similar palladium silicotungstate crystal structures Cs3K2Na4[Cs 2K(H2O)7PdII 2WO(H 2O)A-α-SiW9O34)2]•5H 2O (1) and Cs9Na5[PdII 3Si2W18O69]•20H2O (2). This is the first report of having two complexes so closely related by structure where the only difference in preparation is the concentration of counter cation added. Chapter two describes an iron silicotungstate compound [(CH3)2NH2] 6[β-FeIII 2SiW10O36(OH) 2Cl2]•8H2O•0.5[(CH3) 2NH2Cl] (3) a structurally similar compound to that of a reported literature compound [(CH3)2NH2)] 5β-SiFe2W10O36(OH)2(H 2O)Cl]•7H2O (4). Compound 3 is formed following the same literature procedure as 4 but by added more tetra ethyl amine hydrochloride counter cation, 3 is formed. Further studies were performed exchange the chloride atoms for azides.

Table of Contents

List of Figures List of Tables

Chapter 1 Palladium silicotungstates

Introduction...1 Experimental...6

Synthesis of Cs3K2Na4[Cs2K(H2O)7PdII2WO(H2O)(A-α-SiW9O34)2]•5H2O...6 Synthesis of Cs9Na5[PdII3(SiW9O34)2]•16H2O...12

Results and Discussion...17

Confirmation that structure 1 is the same as that reported by Kortz et al. Cs3K2Na4[Cs2K(H2O)7PdII2WO(H2O)(A-α-SiW9O34)2]•5H2O...17 Synthesis and structure of di- and tri- Palladium Sandwich POMs, 1 and 2...19 Effect of Cs+ countercation in the synthesis of 1 and 2...21

Chapter 2 Iron silicotungstate

Introduction...25 Experimental...26

Synthesis of [(CH3)2NH2]6[β-FeIII2SiW10O36(OH)2Cl2]•8H2O•0.5[(CH3)2NH2Cl]...27

Results and Discussion...31

Synthesis and structure of iron silicotungstate...31 Exchange of the two terminally bound chloride ions...33


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