与双（二苯基膦基）（<i>N-</i>硫醚）胺组装配体的两性离子钴配合物：结构，EPR，磁性和计算研究。,Inorganic Chemistry

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与双（二苯基膦基）（N-硫醚）胺组装配体的两性离子钴配合物：结构，EPR，磁性和计算研究。
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2016-04-07 00:00:00 , DOI: 10.1021/acs.inorgchem.5b02889
Christophe Fliedel , Vitor Rosa , Bertrand Vileno ₁ , Nathalie Parizel , Sylvie Choua , Christophe Gourlaouen , Patrick Rosa ₂ , Philippe Turek , Pierre Braunstein

Affiliation

带有烷基硫醚或芳硫醚N-取代基（Ph ₂ P）₂ N（CH ₂）₃ SMe（1）和（Ph ₂ P）的N-官能化DPPA型的两个杂官能P，P和S配位基研究了分别朝向二氯化钴的₂ N（p -C ₆ H ₄）SMe（2），以研究P N P氮与S原子之间的连接基的影响。络合物[CoCl ₂（1）] ₂（3）和[CoCl ₂（2）] ₂（4）已被分离，X射线衍射显示3为独特的双核两性离子，包含一个被两个配体双螯合的CoCl部分。1和一个由硫醚官能团的S原子配位的CoCl ₃片段。的FT-IR，UV-VIS，和EPR光谱特征3进行分析那些由一个逆合成型的分析，鉴定组成性片段的叠加。一种类似的方法可以洞悉4的本质因此无法获得X射线衍射数据。的分光之间的比较提供4和它的组成片段，[氯化钴（2）₂ ] PF ₆（7）和[H 2 '] ₂ [氯化钴₄ ]（8）（2 '= NH ₂（p -C ₆ H ₄）SMe），以及介于4和3之间的那些表明4可以具有两性离子结构，类似于3，或包含与CoCl ₄二价阴离子相关的四面体双螯合Co中心。进行了磁和EPR研究以及理论计算。发现五配位配合物[CoCl（1）₂ ] PF ₆（5）和7的双峰自旋态和四面体配合物[CoCl ₃（H 1）]（6）（1）= NH _2的各向异性四重态自旋态。（CH ₂）₃ SMe）和8。对于3和4，观察到非常相似的行为，由非相互作用的双峰和四峰自旋态并列组成。反铁磁相互作用解释了六聚体和8层的二聚体的形成。3和4的EPR标记分别对应于5和7中的低旋核和6和8中的高旋核的叠加。从DFT计算得出，固态结构4最能描述为两性离子，且Co1原子具有低自旋态。

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Zwitterionic Cobalt Complexes with Bis(diphenylphosphino)(N-thioether)amine Assembling Ligands: Structural, EPR, Magnetic, and Computational Studies

The coordination of two heterofunctional P,P,S ligands of the N-functionalized DPPA-type bearing an alkylthioether or arylthioether N-substituent, (Ph₂P)₂N(CH₂)₃SMe (1) and (Ph₂P)₂N(p-C₆H₄)SMe (2), respectively, toward cobalt dichloride was investigated to examine the influence of the linker between the PNP nitrogen and the S atoms. The complexes [CoCl₂(1)]₂ (3) and [CoCl₂(2)]₂ (4) have been isolated, and 3 was shown by X-ray diffraction to be a unique dinuclear, zwitterion containing one CoCl moiety bis-chelated by two ligands 1 and one CoCl₃ fragment coordinated by the S atom of a thioether function. The FT-IR, UV–vis, and EPR spectroscopic features of 3 were analyzed as the superposition of those of constitutive fragments identified by a retrosynthetic-type analysis. A similar approach provided insight into the nature of 4 for which no X-ray diffraction data could be obtained. A comparison between the spectroscopic features of 4 and of its constitutive fragments, [CoCl(2)₂]PF₆ (7) and [H2′]₂[CoCl₄] (8) (2′ = NH₂(p-C₆H₄)SMe), and between those of 4 and 3 suggested that 4 could either have a zwitterionic structure, similar to that of 3, or contain a tetrahedral dicationic bis-chelated Co center associated with a CoCl₄ dianion. Magnetic and EPR studies and theoretical calculations were performed. Doublet spin states were found for the pentacoordinated complexes [CoCl(1)₂]PF₆ (5) and 7 and anisotropic quadruplet spin states for the tetrahedral complexes [CoCl₃(H1′)] (6) (1′ = NH₂(CH₂)₃SMe) and 8. A very similar behavior was observed for 3 and 4, consisting in the juxtaposition of noninteracting doublet and quadruplet spin states. Antiferromagnetic interactions explain the formation of dimers for 6 and of layers for 8. The EPR signatures of 3 and 4 correspond to the superposition of low-spin nuclei in 5 and 7 and high-spin nuclei in 6 and 8, respectively. From DFT calculations, the solid-state structure of 4 appears best described as zwitterionic, with a low-spin state for the Co1 atom.

更新日期：2016-04-07

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