Abstract The new (AsPh4)2[ReF6]·2H2O salt was prepared by metathesis from the reaction of (NH4)2ReF6 and (AsPh4)Cl in water and characterized by single crystal X-ray diffraction and UV–Visible spectroscopy. (AsPh4)2[ReF6]·2H2O crystallizes in the space group P 1 ¯ (a = 10.0609(17) A, b = 11.0577(18) A, c = 21.184(4) A, α = 75.974(2) °, β = 77.922(2) °, γ = 71.396(2) °). In (AsPh4)2[ReF6]·2H2O, the ReF62- anion exhibits a slightly distorted octahedral geometry with Re F = 1.9470(12) A − 1.9693(13) A and Re F> = 88.44(6) ° − 91.88(6) °. The reaction of (AsPh4)2[ReF6]·2H2O with triphenylphosphine and trifluoroacetic acid in acetonitrile produced a new Re(+5) oxo-fluoride complexes, ReOF(OOCCF3)2(PPh3)2. ReOF(OOCCF3)2(PPh3)2 exhibits a distorted octahedral geometry and consists of a [ReOF]2+ core coordinated to two trans-PPh3 and two trans- CF3COO- ligands. In ReOF(OOCCF3)2(PPh3)2 , the F and O atoms are statistically disordered. The O/F position (Re O/F = 1.7947(23) A) are equally occupied by 9-electron F atoms (Re F distance of 1.924(10) A and 8-electron O atoms (Re O = 1.682(11) A). The UV–Visible spectrum of ReOF(OOCCF3)2(PPh3)2 in acetonitrile is consistent with the one of Re(+5) oxo-complexes; it exhibits bands at 260 nm, 365 nm and 530 nm that has been respectively attributed to (P) → (Re) and (O) → (Re) transitions as well as transitions in the ligand field.

中文翻译：

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通过三氟乙酸辅助的六氟铼（IV）阴离子途径制备中价铼氟膦配合物

摘要 通过(NH4)2ReF6 和(AsPh4)Cl 在水中的复分解反应制备了新的(AsPh4)2[ReF6]·2H2O 盐，并通过单晶X 射线衍射和紫外-可见光谱对其进行了表征。(AsPh4)2[ReF6]·2H2O 在空间群 P 1 ¯ (a = 10.0609(17) A, b = 11.0577(18) A, c = 21.184(4) A, α = 75.974(2) °, β = 77.922(2)°，γ = 71.396(2)°)。在 (AsPh4)2[ReF6]·2H2O 中，ReF62- 阴离子表现出轻微扭曲的八面体几何形状，Re F = 1.9470(12) A − 1.9693(13) A 和 Re F> = 88.44(6) ° − 91.88(6 )°。(AsPh4)2[ReF6]·2H2O 与三苯基膦和三氟乙酸在乙腈中的反应生成了一种新的 Re(+5) 氧氟配合物 ReOF(OOCCF3)2(PPh3)2。ReOF(OOCCF3)2(PPh3)2 表现出扭曲的八面体几何形状，并由与两个反式-PPh3 和两个反式-CF3COO-配体配位的 [ReOF]2+ 核组成。在 ReOF(OOCCF3)2(PPh3)2 中，F 和 O 原子在统计上是无序的。O/F 位置 (Re O/F = 1.7947(23) A) 被 9 电子 F 原子 (Re F 距离为 1.924(10) A 和 8 电子 O 原子 (Re O = 1.682(11) A). 乙腈中 ReOF(OOCCF3)2(PPh3)2 的紫外-可见光谱与 Re(+5) 氧合络合物之一一致；它在 260 nm、365 nm 和 530 nm 处表现出带分别归因于 (P) → (Re) 和 (O) → (Re) 跃迁以及配体场中的跃迁。