Complexes of Cobalt(II) Chloride with the Tripodal Trisphosphane triphos: Solution Dynamics, Spin-Crossover, Reactivity, and Redox Activity
Complexes of Cobalt(II) Chloride with the Tripodal Trisphosphane triphos: Solution Dynamics, Spin-Crossover, Reactivity, and Redox Activity
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氯化钴 (II) 与三磷三磷的配合物：溶液动力学、自旋交叉、反应性和氧化还原活性
DOI：
10.1021/ic9705352
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发表时间：
1997
影响因子：
4.6
通讯作者：
P. Schober
中科院分区：
文献类型：
--
作者：
K. Heinze;G. Huttner;L. Zsolnai;P. Schober
根据反应条件的不同，CoCl2与CH3C(CH2PPh2)3 （triphos）反应得到不同的产物，包括低自旋配合物[(triphos)Co(μ-Cl)2Co(triphos)]2+(12+)和[(triphos)CoCl2](3)，用x射线法测定了它们的固体结构。此外，溶液中还存在四坐标高自旋配合物[（η - 2-三磷）CoCl2](2)，其相对于3的浓度取决于溶剂和温度。研究了这些物质对路易斯酸的反应性，生成了新的异双核配合物[(triphos)Co(μ-Cl)2MCl2] (M = Fe （5), Co(6)）。与路易斯碱L反应生成稀有类型的配合物[（三磷酸）CoCl(L)]+ (L = CO (7+), PMe3 (8+), NH3 （9+), CH3CN(10+)）。单电子还原3得到先前制备的假四面体[(triphos)CoICl]配合物11，单电子氧化得到新的三角-双锥体低自旋配合物[(triphos)CoIIICl2]+(12+)。
Depending on the reaction conditions, different products are obtained from the reaction of CoCl2 with CH3C(CH2PPh2)3 (triphos), including the low-spin complexes [(triphos)Co(μ-Cl)2Co(triphos)]2+ (12+) and [(triphos)CoCl2] (3), their solid-state structures being determined by X-ray methods. In solution, additionally, a four-coordinate high-spin complex [(η2-triphos)CoCl2] (2) is present, its concentration relative to that of 3 depending on the solvent and the temperature. The reactivity of these species toward Lewis acids is investigated leading to the novel heterodinuclear complexes [(triphos)Co(μ-Cl)2MCl2] (M = Fe (5), Co (6)). Reactions with Lewis bases L yield complexes of the rare type [(triphos)CoCl(L)]+ (L = CO (7+), PMe3 (8+), NH3 (9+), CH3CN (10+)). One-electron reduction of 3 leads to the previously prepared pseudotetrahedral [(triphos)CoICl] complex 11, and one-electron oxidation to the novel trigonal-bipyramidal low-spin complex [(triphos)CoIIICl2]+ (12+).