Methanesulfonates of High‐Valent Metals: Syntheses and Structural Features of MoO 2 (CH 3 SO 3 ) 2 , UO 2 (CH 3 SO 3 ) 2 , ReO 3 (CH 3 SO 3 ), VO(CH 3 SO 3 ) 2 , and V 2 O 3 (CH 3 SO 3 ) 4 and Their Thermal Decomposition under N 2 and O 2 Atmosphere

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO 3 , UO 2 (CH 3 COO) 2 ⋅ 2 H 2 O, Re 2 O 7 (H 2 O) 2 , and V 2 O 5 with CH 3 SO 3 H or mixtures thereof with its anhydride. These compounds are the first examples of solvent‐free oxide methanesulfonates of these elements. MoO 2 (CH 3 SO 3 ) 2 ( Pbca , a =1487.05(4), b =752.55(2), c =1549.61(5) pm, V =1.73414(9) nm 3 , Z =8) contains [MoO 2 ] moieties connected by [CH 3 SO 3 ] ions to form layers parallel to (100). UO 2 (CH 3 SO 3 ) 2 ( P 2 1 / c , a =1320.4(1), b =1014.41(6), c =1533.7(1) pm, β =112.80(1)°, V =1.8937(3) nm 3 , Z =8) consists of linear UO 2 2+ ions coordinated by five [CH 3 SO 3 ] ions, forming a layer structure. VO(CH 3 SO 3 ) 2 ( P 2 1 / c , a =1136.5(1), b =869.87(7), c =915.5(1) pm, β =113.66(1)°, V =0.8290(2) nm 3 , Z =4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO 3 (CH 3 SO 3 ) ( ${P\bar 1}$ , a =574.0(1), b =1279.6(3), c =1641.9(3) pm, α =102.08(2), β =96.11(2), γ =99.04(2)°, V =1.1523(4) nm 3 , Z =8) a chain structure exhibiting infinite O[ReO 2 ]O[ReO 2 ]O chains is formed. Each [ReO 2 ]O[ReO 2 ] unit is coordinated by two bidentate [CH 3 SO 3 ] ions. V 2 O 3 (CH 3 SO 3 ) 4 ( I 2/ a , a =1645.2(3), b =583.1(1), c =1670.2(3) pm, β =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 [CH 3 SO 3 ] ligands. Additional methanesulfonate ions connect the [V 2 O 3 ] 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 MoO 2 , U 3 O 7 , V 4 O 7 , and VO 2 ; for MoO 2 (CH 3 SO 3 ) 2 , a small amount of MoS 2 is formed. If the thermal decomposition is carried out in a atmosphere of O 2 the oxides MoO 3 and V 2 O 5 are formed.