Abstract

Four new representatives of potassium fluorotrifluoroacetatometallates are synthesized and crystallographically studied: K₂[Co₃(µ₃-F)(CF₃COO)₆(CF₃COO)(CF₃COOH)₂]·CF₃COOH (I), K[Co₃(µ₃-F)(CF₃COO)₆(H₂O)₃]·H₂O·2CF₃COOH (II), K[Ni₃(µ₃-F)(CF₃COO)₆(H₂O)₃]·H₂O·2CF₃COOH (III), and K₂[Ni₃(µ₃-F)(CF₃COO)₆(CF₃COOH)₃][Ni₃(µ₃-F)(CF₃COO)₆(CF₃COOH)₂(H₂O)]·CF₃COOH (IV). All complexes under study contain trinuclear triangular complex anions [M₃(µ₃-F)(CF₃COO)₆(L)₃]^n– (M = Ni, Co; L = CF₃COO^–, CF₃COOH, H₂O; n = 1, 2) resembling in structure the earlier studied fluorotrifluoroacetatometallates of alkaline metals and ammonium. The µ₃-bridging F atom is localized at the center of the triangle of the Ni(II) or Co(II) atoms. Six bridging trifluoroacetate groups arranged above and under the plane of the [M₃F] triangle pairwise bind the metal atoms. The oxygen atoms of ligands L supplement the coordination environment of the M atoms to the octahedral environment. The possibility of the charge –2 on the complex anion [M₃(µ₃-F)(CF₃COO)₆L₃] is shown. The consecutive replacement of the axial molecules of trifluoroacetic acid by water changes the type of the structure from the chain (IV) to layered (II, III) structure and then to the volume network (I). The molecular structures of complexes I–IV are determined by X‑ray structure analysis (CIF files CCDC nos. 2010760 (I), 2010761 (II), 2010762 (III), and 2010763(IV)).

中文翻译：

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新型氟三氟乙酰金属化钾的合成和晶体结构：Kn[M3(µ3-F)(CF3COO)6L3]L' (M = Co, Ni; L = CF3COO–, CF3COOH, H2O; L' = CF3COOH, H2O; n = 1 , 2)

摘要

合成和晶体学研究了四种新的氟三氟乙酰金属酸钾代表物：K ₂ [Co ₃ (µ ₃ -F)(CF ₃ COO) ₆ (CF ₃ COO)(CF ₃ COOH) ₂ ]·CF ₃ COOH ( I ), K [Co ₃ (µ ₃ -F)(CF ₃ COO) ₆ (H ₂ O) ₃ ]·H ₂ O·2CF ₃ COOH ( II ), K[Ni ₃ (µ ₃ -F)(CF ₃ COO) ₆（H₂ O) ₃ ]·H ₂ O·2CF ₃ COOH ( III ) 和 K ₂ [Ni ₃ (μ ₃ -F)(CF ₃ COO) ₆ (CF ₃ COOH) ₃ ][Ni ₃ (μ ₃ -F) )(CF ₃ COO) ₆ (CF ₃ COOH) ₂ (H ₂ O)]·CF ₃ COOH ( IV )。研究中的所有配合物都含有三核三角形配合物阴离子 [M ₃ (µ ₃ -F)(CF ₃ COO) ₆ (L)₃ ] ^{n –} (M = Ni, Co; L = CF ₃ COO ^– , CF ₃ COOH, H ₂ O; n = 1, 2) 在结构上类似于早期研究的碱金属和铵的氟三氟乙酰金属化物。µ ₃桥接 F 原子位于 Ni(II) 或 Co(II) 原子三角形的中心。排列在 [M ₃ F] 三角形平面上方和下方的六个桥接三氟乙酸酯基团成对地结合金属原子。配体 L 的氧原子将 M 原子的配位环境补充到八面体环境中。复合阴离子上电荷 –2 的可能性 [M ₃ (µ ₃显示了-F)(CF ₃ COO) ₆ L ₃ ]。三氟乙酸的轴向分子被水连续置换，结构类型从链状（IV）变为层状（II、III）结构，再到体积网络（I）。配合物I - IV的分子结构由 X 射线结构分析确定（CIF 文件 CCDC 编号 2010760（I）、2010761（II）、2010762（III）和 2010763（IV））。