The first oxalate-bridged one-dimensional polymer containing MoV2 dimers with single metal–metal bonds. Syntheses and structures of (MeNC<sub>5</sub>H<sub>5</sub>)<sub>2</sub><sub>n</sub>[Mo<sub>2</sub>O<sub>4</sub>(C<sub>2</sub>O<sub>4</sub>)Cl<sub>2</sub>]n and (3-MePyH)<sub>2</sub><sub>n</sub>[Mo<sub>2</sub>O<sub>4</sub>(C<sub>2</sub>O<sub>4</sub>)Cl<sub>2</sub>]<sub>n</sub>
作者:Barbara Modec、Jurij V. Brenčič、Darko Dolenc、Jon Zubieta
DOI:10.1039/b207544j
日期:——
Hydrothermal reactions of mononuclear oxochloromolybdate(V) with oxalic acid in alcohol (methanol or 2-propanol) and pyridines (pyridine or 3-methylpyridine) media have afforded two polymeric compounds of molybdenum(V): N-methylpyridinum catena-μ-oxalato-O1,O2:O1â²,O2â²-(dichloro-di-μ-oxo-dioxodimolybdate(V)), (MeNC5H5)2n[Mo2O4(C2O4)Cl2]n1 and 3-methylpyridinium catena-μ-oxalato-O1,O2:O1â²,O2â²-(dichloro-di-μ-oxo-dioxodimolybdate(V)), (3-MePyH)2n[Mo2O4(C2O4)Cl2]n2. The compounds were fully characterized by X-ray structural analysis, infrared and NMR spectroscopy. The essentially isostructural anionic chains in 1and 2 are built of alternating pairs of Mo2O4}2+ containing edge-sharing octahedra and planar oxalates giving a Mo â¶ oxalate ratio of 2. The bisbidentate oxalate acts as a bridge between two dinuclear subunits. The formation of a N-methylpyridinium cation from methanol and pyridine in the presence of molybdenum(V) and oxalic acid has not been documented before.
单核氯代钼酸盐(V)与草酸在乙醇(甲醇或2-丙醇)和吡啶(吡啶或3-甲基吡啶)介质中发生水热反应,得到两种钼(V)聚合物:N-甲基吡啶链-μ-草酸根- O1,O2:O1‐,O2‐‐(二氯-二-μ-氧代-二氧二钼酸盐(V)), (MeNC5H5)2n[Mo2O4(C2O4)Cl2]n1 和 3-甲基吡啶链-μ-草酸-O1 ,O2:O1-,O2--(二氯-二-μ-氧代-二氧二钼酸盐(V)),(3-MePyH)2n[Mo2O4(C2O4)Cl2]n2。通过X射线结构分析、红外光谱和核磁共振光谱对这些化合物进行了充分表征。 1和2中基本上同构的阴离子链由交替对的Mo2O4}2+组成,包含边缘共享八面体和平面草酸盐,Mo与草酸盐的比率为2。二齿草酸盐充当两个双核亚基之间的桥梁。在钼(V)和草酸存在下,甲醇和吡啶形成 N-甲基吡啶鎓阳离子之前尚未有文献报道。