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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Studies of new volatile copper(I) complexes with triphenylphosphite and perfluorinated carboxylates
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Studies of new volatile copper(I) complexes with triphenylphosphite and perfluorinated carboxylates

机译：亚磷酸三苯酯和全氟化羧酸盐的新型挥发性铜（I）配合物的研究

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摘要

Copper(I) complexes with triphenylphosphite and aliphatic perfluorinated carboxylates of the type [Cu(#mu#-RCOO){P(OC_6H_5)_3}]_2, where R = CF_3, C_2F_5, C_3F_7, C_6F_(13), C_7F_(15), C_8F_(17) and C_9F_(19) have been prepared as viscous liquids and characterised by ~(13)C, ~(19)F, ~(31)P, ~(63)Cu NMR, IR and mass spectra. In the liquid state, a dimeric structure with Cu in trigonal symmetry linked by the bridging carboxylates is proposed. Temperature-dependent ~(31)P and ~(63)Cu NMR spectra were determined, in the 333-233 K range and single lines from both nuclei were detected, suggesting the fast exchange of triphenylphosphite in acetonitrile solution. Copper relaxation is sufficiently slow to record the signal, which is the first time that this has been reported for complexes with P(OC_6H_5)_3. Examination of ~(13)C and ~(19)F resonances confirm coordination of carboxylates in solution where few dimeric species with a geometry lower than T_d symmetry can exist. Thermal decomposition of complexes proceeds as a multistage process, yielding a mixture of Cu, Cu_2O and Cu_2P_2O_7.
机译：铜（I）与亚磷酸三苯酯和[Cu（＃mu＃-RCOO）{P（OC_6H_5）_3}] _ 2型脂族全氟化羧酸盐的络合物，其中R = CF_3，C_2F_5，C_3F_7，C_6F_（13），C_7F_（15 ），C_8F_（17）和C_9F_（19）已制备为粘性液体，并通过〜（13）C，〜（19）F，〜（31）P，〜（63）Cu NMR，IR和质谱进行了表征。在液态下，提出了通过桥连的羧酸盐连接具有三角形对称Cu的二聚体结构。在333-233 K范围内测定了温度相关的〜（31）P和〜（63）Cu NMR光谱，并检测到来自两个核的单线，表明亚磷酸三苯酯在乙腈溶液中的快速交换。铜弛豫足够慢，无法记录信号，这是首次报道P（OC_6H_5）_3的配合物。对〜（13）C和〜（19）F共振的检查证实了溶液中羧酸盐的配位，其中几乎不存在几何形状低于T_d对称性的二聚体。配合物的热分解是一个多阶段过程，产生了Cu，Cu_2O和Cu_2P_2O_7的混合物。

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