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Site preferences in hetero-metallic [Fe9−xNix] clusters: a combined crystallographic, spectroscopic and theoretical analysis
Dalton Transactions ( IF 3.5 ) Pub Date : 2017-09-11 00:00:00 , DOI: 10.1039/c7dt02930f
Anastasia N. Georgopoulou 1, 2, 3, 4 , Karrar Al-Ameed 5, 6, 7, 8, 9 , Athanassios K. Boudalis 1, 2, 3, 4, 10 , Dimitrios F. Anagnostopoulos 4, 11, 12, 13 , Vassilis Psycharis 1, 2, 3, 4 , John E. McGrady 5, 6, 7 , Yiannis Sanakis 1, 2, 3, 4 , Catherine P. Raptopoulou 1, 2, 3, 4
Affiliation  

The reaction of mixtures of Fe(O2CMe)2·2H2O and Ni(O2CMe)2·4H2O of various compositions with di-2-pyridyl ketone (py2CO, dpk) in MeCN under an inert atmosphere afforded a family of hetero-metallic enneanuclear clusters with general formula [Fe9−xNix4-OH)2(O2CMe)8(py2CO2)4] (2, x = 1.00; 3: x = 6.02; 4, x = 7.46; 5, x = 7.81). Clusters 2–5 are isomorphous to the homo-metallic [Fe9] cluster (1) previously reported by some of us, and also isostructural to the known homo-metallic [Ni9] cluster. All four clusters contain a central MII ion in an unusual 8-coordinate site and eight peripheral MII ions in distorted octahedral environments. The distribution of FeII and NiII ions over these two distinct coordination sites in 2–5 can be established through a combination of X-ray fluorescence and Mössbauer spectroscopies, which show that FeII preferentially occupies the unique 8-coordinate metal site while NiII accumulates in the octahedral holes. Density functional theory indicates that the distribution of ions across the two sites arises not from any intrinsic preference of the FeII ions for the 8-coordinate sites, but rather because of the large ligand field stabilization energy available to NiII in octahedral coordination.

中文翻译:

异金属[Fe 9− x Ni x ]团簇中的位点偏好:晶体学,光谱学和理论分析的组合

惰性条件下,各种组成的Fe(O 2 CMe)2 ·2H 2 O和Ni(O 2 CMe)2 ·4H 2 O的混合物与二-2-吡啶基酮(py 2 CO,dpk)在惰性气体中的反应气氛,得到一个家庭与通式异质金属enneanuclear簇的[Fe 9- X的Ni X(μ 4 -OH)2(O 2 CME)8(PY 2 CO 24 ](2X = 1.00; 3x = 6.02;4x = 7.46;5x= 7.81)。团簇2–5与我们中某些人先前报道的同金属[Fe 9 ]团簇(1)同构,并且与已知的同金属[Ni 9 ]团簇同构。所有四个簇都在一个不寻常的8坐​​标位置包含一个中心M II离子,并且在扭曲的八面体环境中包含八个外围M II离子。Fe II和Ni II离子在2–5中这两个不同的配位点上的分布可以通过X射线荧光和Mössbauer光谱学的组合来建立,这表明Fe II优先占据独特的8坐标金属位点,而Ni II则积累在八面体孔中。密度泛函理论表明,离子在两个位点上的分布不是由Fe II离子对8位配位点的内在偏好引起的,而是由于Ni II在八面体配位中具有较大的配体场稳定能。
更新日期:2017-09-18
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