Abstract

The first iodide cluster of molybdenum with the metal cage in the form of a tetragonal pyramid (Bu₄N)[Mo₅OI₁₃]·THF (I) and cocrystallizate (Bu₄N){[Mo₅OI₁₃]_0.9[Mo₆I₁₄]·THF (II) are synthesized for the first time by heating a LiI–I₂–Mo mixture in a temperature range of 300–400°С followed by the extraction of the product. Complexes I and II are studied by X-ray diffraction analysis (CIF files CCDC nos. 2063029 (I) and 2063030 (II)). The molybdenum atoms in [Mo₅OI₁₃]^– form a square pyramid with Mo–Mo distances of 2.67 Å between the basal molybdenum atoms and the Mo–Mo distances equal to 2.72 Å between the apical and basal molybdenum atoms. The oxygen atom is coordinated to the pyramid base (Mo–μ₄-O 2.10 Å). The cluster anion [Mo₅OI₁₃]^– can be presented as the octahedral cluster anion [Mo₆I₁₄]^2– in which the position of the {MoI}^– fragment (d⁰, 6e) is occupied by the isoelectronic oxygen atom (s²p⁴, 6e). In the structure of compound II, the [Mo₅OI₁₃]^– and [Mo₆I₁₄]^2– cluster anions occupy close atomic positions.

中文翻译：

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第一个五核碘化钼簇 (Bu4N)[Mo5OI13]：合成和结构

摘要

钼的第一个碘化物簇与金属笼呈四方锥 (Bu ₄ N)[Mo ₅ OI ₁₃ ]·THF ( I ) 和共结晶 (Bu ₄ N){[Mo ₅ OI ₁₃ ] _0.9 [Mo ₆ I ₁₄ ]·THF ( II ) 通过在 300-400°С 的温度范围内加热 LiI-I ₂ -Mo 混合物，然后提取产物，首次合成。配合物I和II通过 X 射线衍射分析（CIF 文件 CCDC 编号 2063029 ( I ) 和 2063030 ( II)))。在钼原子[沫₅ OI ₁₃ ] ^-形成正方形棱锥与基础钼原子和钼-钼距离之间2.67埃的钼-钼的距离等于所述顶端和基底钼原子之间2.72埃。氧原子与金字塔基（Mo-μ ₄ -O 2.10 Å）配位。团簇阴离子 [Mo ₅ OI ₁₃ ] ^–可以表示为八面体团簇阴离子 [Mo ₆ I ₁₄ ] ^2–其中 {MoI} ^–碎片 ( d ⁰ , 6e) 的位置被等电子氧原子占据( s ² p⁴，6E）。在化合物II的结构中，[Mo ₅ OI ₁₃ ] ^-和[Mo ₆ I ₁₄ ] ^2-簇阴离子占据接近的原子位置。