Unligated Diruthenium(II,II) Tetra(trifluoroacetate): The First X-ray Structural Study, Thermal Compressibility, Lewis Acidity, and Magnetism
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- 作者：Evgeny V. Dikarev ; Alexander S. Filatov ; Rodolphe Clé ; rac ; and Marina A. Petrukhina
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：January 23, 2006
- 年：2006
- 卷：45
- 期：2
- 页码：744 - 751
- 全文大小：303K
- 年卷期：v.45,no.2(January 23, 2006)
- ISSN：1520-510X
文摘
The title compound, [Ru2(O2CCF3)4] (1), has been obtained without any exogenous ligands and crystallized bydeposition from the gas phase at 170 
C. Its crystal structure has been determined for the first time to confirm aninfinite chain motif built on axial Ru···O interactions of the diruthenium(II,II) units. The X-ray diffraction studies atvariable temperatures showed no phase transitions in the range of 295-100 K but revealed a significant decreasein the volume per atom from 14.2 to 13.3 Å3. This noticeable thermal compressibility effect is discussed in connectionwith the solid-state packing of the [Ru2(O2CCF3)4]
chains. The highly electrophilic character of the diruthenium(II,II) units has been shown by the gas-phase deposition reaction of [Ru2(O2CCF3)4] with an aromatic donor substrate,namely [2.2]paracyclophane (C16H16). As a result of the above reaction, a new arene adduct [Ru2(O2CCF3)4·C16H16] (2) has been isolated in crystalline form. It has an extended one-dimensional (1D) chain structure comprisedof alternating building units and based on the rare bridging mode of [2.2]paracyclophane, [Ru2(O2CCF3)4·(
2-
2:2-C16H16)]. The magnetic susceptibility of 1 and 2 has been measured and compared in the range of 1.8-300K. In addition, in the course of synthesis of 1 by the carboxylate exchange reactions, a new mixed-carboxylatediruthenium(II,II) core complex [Ru2(O2CCF3)3(O2CC2H5)] (3), bearing no exogenous ligands, has also been isolatedand structurally characterized. It exhibits an interesting polymeric structure in which the ruthenium(II) centers selectivelyform axial interdimer contacts with the O-atoms of the propionate groups only.
C. Its crystal structure has been determined for the first time to confirm aninfinite chain motif built on axial Ru···O interactions of the diruthenium(II,II) units. The X-ray diffraction studies atvariable temperatures showed no phase transitions in the range of 295-100 K but revealed a significant decreasein the volume per atom from 14.2 to 13.3 Å3. This noticeable thermal compressibility effect is discussed in connectionwith the solid-state packing of the [Ru2(O2CCF3)4] chains. The highly electrophilic character of the diruthenium(II,II) units has been shown by the gas-phase deposition reaction of [Ru2(O2CCF3)4] with an aromatic donor substrate,namely [2.2]paracyclophane (C16H16). As a result of the above reaction, a new arene adduct [Ru2(O2CCF3)4·C16H16] (2) has been isolated in crystalline form. It has an extended one-dimensional (1D) chain structure comprisedof alternating building units and based on the rare bridging mode of [2.2]paracyclophane, [Ru2(O2CCF3)4·(2-2:2-C16H16)]. The magnetic susceptibility of 1 and 2 has been measured and compared in the range of 1.8-300K. In addition, in the course of synthesis of 1 by the carboxylate exchange reactions, a new mixed-carboxylatediruthenium(II,II) core complex [Ru2(O2CCF3)3(O2CC2H5)] (3), bearing no exogenous ligands, has also been isolatedand structurally characterized. It exhibits an interesting polymeric structure in which the ruthenium(II) centers selectivelyform axial interdimer contacts with the O-atoms of the propionate groups only.