Methanesulfonates of High-Valent Metals: Syntheses and Structural Features of MoO2(CH3SO3)(2), UO2(CH3SO3)(2), ReO3(CH3SO3), VO(CH3SO3)(2), and V2O3(CH3SO3)(4) and Their Thermal Decomposition under N-2 and O-2 Atmosphere

作者：Betke Ulf; Neuschulz Kai; Wickleder Mathias S^*

来源：Chemistry - A European Journal, 2011, 17(45): 12784-12801.

DOI：10.1002/chem.201101618

• solid-state structures
• oxide methanesulfonates
• refractory metals
• solvothermal synthesis
• uranium

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO3, UO2(CH3COO)(2)center dot 2H(2)O, Re2O7(H2O)(2), and V2O5 with CH3SO3H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO2(CH3SO3)(2) (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm(3), Z=8) contains [MoO2] moieties connected by [CH3SO3] ions to form layers parallel to (100). UO2(CH3SO3)(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, beta=112.80(1)degrees, V=1.8937(3) nm(3), Z=8) consists of linear UO22+ ions coordinated by five [CH3SO3] ions, forming a layer structure. VO(CH3SO3)(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, beta=113.66(1)degrees, V=0.8290(2) nm(3), Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO3(CH3SO3) (P (1) over bar, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, alpha=102.08(2), beta=96.11(2), gamma=99.04(2) 8, V=1.1523(4) nm(3), Z=8) a chain structure exhibiting infinite O-[ReO2]-O-[ReO2]-O chains is formed. Each [ReO2]-O-[ReO2] unit is coordinated by two bidentate [CH3SO3] ions. V2O3(CH3SO3)(4) (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, beta=102.58(3), V=1.5637(5) pm(3), Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH3SO3] ligands. Additional methanesulfonate ions connect the [V2O3] groups along [001]. Thermal decomposition of the compounds was monitored under N-2 and O-2 atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N-2 the decomposition proceeds with reduction of the metal leading to the oxides MoO2, U3O7, V4O7, and VO2; for MoO2(CH3SO3)(2), a small amount of MoS2 is formed. If the thermal decomposition is carried out in a atmosphere of O-2 the oxides MoO3 and V2O5 are formed.

• 出版日期2011-11-4