Main-Group Element, Organic, and Organometallic Derivatives of Polyoxometalates

Abstract

ContentsI. Introduction 77 II. Scope and Organization of the Review 78 III. Polyoxometalates Incorporating Halides 79 IV. Polyoxometalates Incorporating Group 16 Element-Centered Ligands 81 A. Peroxopolyoxometalates 81 B. Polyoxoalkoxometalates 82 1. Polyoxoalkoxometalates Involving Unidentate Alcohols 82 2. Polyoxoalkoxometalates Involving Chelating Triols 83 C. Heavier Group 16 Element-Centered Ligands 85 1. Thiopolyoxometalates 85 2. Organosulfur and Organoselenium Ligands 85 V. Polyoxometalates Incorporating Group 15 Element-Centered Ligands 86 A. Singly Bonded Nitrogen-Donating Ligands 86 1. Amine and Related Ligands 86 2. Amide Oximes [RC(NH 2 )NOH] and Oximes 87 B. Multiply Bonded Nitrogen Ligands 89 1. Nitrido Derivatives 89 2. Organoimido Derivatives 89 3. Hydrazido and Diazenido Derivatives of Polyoxometalates 90 4. Nitrosyl Derivatives 92 C. Organophosphorus, Organoarsenic, and Organoantimony Ligands 94 1. Organophosphonate and Organoarsonate Ligands 94 2. Organophosphinate and Organoarsinate Ligands 97 VI. Polyoxometalates Incorporating Group 14 Element-Centered Ligands 97 A. Oxocarbon Ligands 97 1. Carbonate 97 2. Carboxylates 97 3. Oxalate and Squarate 97 4. Carbonyl Derivatives 98 B. Silicon Derivatives 98 C. Germanium Derivatives 99 D. Tin and Lead Derivatives 99 VII. Organometallic Derivatives of Polyoxometalates 100 A. Cyclopentadienyl Derivatives of Polyoxometalates 100 B. Cyclopentadienyl Oxide Clusters of Groups 5 and 6 100 C. Organometallic Polyoxometalates 100 1. Polyoxometalate-incorporated Organometalic Complexes 101 2. Polyoxometalate-Supported Organometallic Complexes 101 3. Integrated Cubane-Type Clusters 105 4. Organometallic Cation Salts of Keggin-Type Anions 105 VIII. Concluding Remarks 106 IX. Acknowledgments 106 X. Abbreviations 106 XI. References 106

Naphthyl-Containing Organophosphonate Derivatives of Keggin-Type Polyoxotungstates

“…The P atoms are bonded to the methylenic C atom from the 1-naphthylmethyl moiety, two O atoms from the POM and one terminal O atom (Table S1), and this bonding scheme results in distorted tetrahedral geometries. Bond Valence Sum Calculations (BVS) [55] 6 , gray octahedra (W, gray); XO 4 , green tetrahedra (X, green); P, violet; O, red; C, black; H, pink; N, cyan. Aromatic and n-butyl H atoms are omitted for clarity.…”

“…The organic derivatization of polyoxometalates (POMs) represents one of the most relevant topics within the chemistry of this well-known family of anionic metal-oxo clusters with applications in current fields of interest such as catalysis, medicine and materials science [1][2][3][4][5]. The resulting organic-inorganic hybrids avoid the processing drawbacks that unmodified POMs can display for…”

Hybrid Organic-Inorganic Materials Based on Polyoxometalates and Ionic Liquids and Their Application in Catalysis

“…Polyoxometalates (POMs) are a class of anionic metal-oxygen clusters built by the connection of [MO] polyhedra of the early transition metals in their highest oxidation states [1,2]. Nevertheless, the strict rules for nomenclature, the polyoxometalate compounds [3], could be referred to also as hetero-or isopolyacids and hetero-or isopolyanions or polyoxoanions.…”

“…The type II hybrids group includes all the organic ligands allowing a direct substitution of oxo group of the POMs, such as alkoxides, carboxylates, organosylil derivatives, and organoamides. Extensive reviews on the advances in the field of type II POMs were reported by Dolbecq et al [1] and Gouzerh and Proust [2] and will not be a subject of this paper. On the contrary, this review will focus on POM derivatives involving nonbonding interactions such as molecular complexes between polyoxometalates and organic substrates and more precisely ionic liquids derived cations forming ionic salts and their application in the field of biphasic and heterogeneous catalysis.…”

From molecular modules to modular materials

“…Due to the high stability of the terminal M-O bond in polyoxomolybdates and -tungstates and the relatively slow ligand-exchange kinetics, especially for polyoxotungstates, chemical routes, which target on covalent modifications of the POM surface often lead to rearranged cluster cores. The prolonged reaction times and the rather vigorous reaction conditions often lead to mixtures of chemical derivatives of the original clusters in only moderate or low yields [70].…”