[Mo5VMo7VIO30(BPO4)2(O3P-Ph)6]5-: A Phenyl-Substituted Molybdenum(V/VI) Boro-Phosphate Polyoxometalate
Authors:
- 12 February 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 42 (5) , 1652-1655
Abstract
The title polyanion is the first hybrid borophosphate−phenylphosphonate polyoxometalate. It was structurally characterized as its imidazolium salt, (C3N2H5)5[Mo12O30(BPO4)2(O3P-Ph)6]·H2O (monoclinic, P21/c, a = 22.120(3) Å, b = 13.042(2) Å, and c = 32.632(4) Å, β = 101.293(3)°), which was synthesized hydrothermally from imidazole, molybdenum oxide and metal, and boric, phosphoric, and phenylphosphonic acids. The anion is the second example of a new class of polyoxometalates that resemble Dawson anions but where the two pole caps of three edge-sharing MoO6 octahedra in the latter are replaced by other units, in this case tetrahedral borate sharing corners with three phenylphosphonic groups, {(OB)(O3P-Ph)3}. The 12 molybdenum atoms forming the two equatorial belts of the cluster are of mixed-valence, five are MoV and seven are MoVI, and the resulting five electrons are delocalized. Four of these electrons are paired according to the temperature dependence of the magnetic susceptibility. The new compound is soluble in a mixture of water and pyridine (in equal volumes) as well as in nitromethane, and the anions are intact in these solutions.Keywords
This publication has 15 references indexed in Scilit:
- A Reduced Polyoxomolybdenum Borophosphate Anion Related to the Wells−Dawson ClustersJournal of the American Chemical Society, 2002
- Organic−Inorganic Hybrids Based on Polyoxometalates. 6.1Syntheses, Structure, and Reactivity of the Bis(tert-butylsilyl)decatungstophosphate [(γ-PW10O36)(t-BuSiOH)2]3-Inorganic Chemistry, 2000
- New Hybrid Covalent Networks Based on Polyoxometalates: Part 1. Hybrid Networks Based on Poly(ethyl methacrylate) Chains Covalently Cross-linked by Heteropolyanions: Synthesis and Swelling PropertiesChemistry of Materials, 2000
- Rhodium−Carbon Bond Formation in Aqueous Solution. Synthesis, Structure, and Reactivity of the Functionalized Heteropolytungstates, [XW11O39RhCH2COOH]5,6- (X = P, Si)Journal of the American Chemical Society, 1998
- New Routes for Multiple Derivatization of Polyoxometalates. Bis(acetato)dirhodium-11-tungstophosphate, [(PO4)W11O35{Rh2(OAc)2}]5-Inorganic Chemistry, 1997
- Polyoxometalate Derivatives with Multiple Organic Groups. 2. Synthesis and Structures of Tris(organotin) α, β-Keggin TungstosilicatesInorganic Chemistry, 1996
- Synthesis, structure, spectroscopic properties, and hydrolytic chemistry of organophosphonoyl polyoxotungstates of formula [C6H5P(O)]2Xn+W11O39(8-n)- (Xn+ = P5+, Si4+)Inorganic Chemistry, 1992
- Synthesis and properties of polyoxometalates based inorganic-organic polymersChemistry of Materials, 1992
- The structure of the 9(18)-heteropoly anion in potassium 9(18)-tungstophosphate, K6(P2W18O62).14H2OActa Crystallographica, 1953
- Structure of the Molecule of 12-Phosphotungstic AcidNature, 1933