二硫代氧酰胺桥接多核镍配合物的合成与表征

Q3 Chemistry Chemistry Pub Date : 2023-10-18 DOI:10.3390/chemistry5040150
Tomohiko Hamaguchi, Ryo Kuraoka, Takumi Yamamoto, Naoya Takagi, Isao Ando, Satoshi Kawata
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引用次数: 0

摘要

混合价配合物含有两种形式氧化数不同的金属,因此,表现出混合性质,这些性质受两种金属之间的电子耦合的影响,而电子耦合反过来又由桥接配体调节。这对许多研究人员来说是一个有吸引力的点。草酸盐被广泛用作制备多核配合物的桥接配体。到目前为止,已经报道了1000多个复合物。然而,作为草酸类似物的二硫氨酯作为桥接配体不太受欢迎。本文建立了一种新的二硫氧嘧啶桥接镍-二膦双核配合物,其分子式为[(μ2-toxa){Ni(dppe)}2](BF4)2 (toxa =二硫氧氧嘧啶;制备了dppe = 1,2-双(二苯基膦)乙烷,并用单晶x射线衍射对其进行了表征。用1,3-双(二苯基膦)丙烷(dppp)代替dppe,得到了双核、三核和四核配合物,即[(μ2-toxa){Ni(dppp)}2](BF4)2、[{μ2-Ni(toxa)2}{Ni(dppp)}2](BF4)2和[{μ3-Ni(toxa)3}{Ni(dppp)}3](BF4)2。双核配合物中的双齿配体以κ(S,N)的形式协调每个Ni原子。然而,三核和四核复合物具有κ(N,N)和κ(S,S)配位的toxa配体。[(μ2-toxa){Ni(dppe)}2](BF4)2配合物经过4个可逆氧化还原过程,在∆E1/2 = 0.22 V下,通过控制电位吸收光谱分析,发现存在Ni(II)-Ni(I)混合价态,比值常数为6.1 × 103。
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Synthesis and Characterization of Dithiooxamidate-Bridged Polynuclear Ni Complexes
Mixed-valence complexes contain two metals with different formal oxidation numbers and, therefore, show mixed properties that are influenced by the electronic coupling between the two metals, which is, in turn, regulated by a bridging ligand. This is an attractive point for many researchers. Oxalate is widely used as a bridging ligand for preparing polynuclear complexes. More than 1000 complexes have been reported until now. However, dithiooxamidate, which is an oxalate analog, is less popular as a bridging ligand. Here, a new dithiooxamidate-bridged Ni-diphosphine dinuclear complex with the formula [(μ2-toxa){Ni(dppe)}2](BF4)2 (toxa = dithiooxamidate; dppe = 1,2-bis(diphenylphosphino)ethane) was prepared and characterized via single-crystal X-ray diffraction. When using 1,3-bis(diphenylphosphino)propane (dppp) instead of dppe, dinuclear, trinuclear, and tetranuclear complexes were obtained, i.e., [(μ2-toxa){Ni(dppp)}2](BF4)2, [{μ2-Ni(toxa)2}{Ni(dppp)}2](BF4)2, and [{μ3-Ni(toxa)3}{Ni(dppp)}3](BF4)2, respectively. Bidentate toxa ligands in dinuclear complexes coordinate each Ni atom as κ(S,N). However, the trinuclear and the tetranuclear complexes have the toxa ligands with κ(N,N) and κ(S,S) coordination. The [(μ2-toxa){Ni(dppe)}2](BF4)2 complex undergoes four reversible redox processes, whose analysis via a controlled-potential absorption spectrum reveals the presence of a Ni(II)-Ni(I) mixed-valence state at ∆E1/2 = 0.22 V with a comproportionation constant of 6.1 × 103.
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CiteScore
2.50
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11 weeks
期刊介绍: Chemistry—A European Journal is a truly international journal with top quality contributions (2017 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields.
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