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Contrasting Structure and Bonding of a Copper-Rich and a Zinc-Rich Intermetalloid Cu/Zn Cluster.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-06-24 , DOI: 10.1021/acs.inorgchem.0c00943 Max Schütz 1, 2 , Maximilian Muhr 1, 2 , Kerstin Freitag 1 , Christian Gemel 1, 2 , Samia Kahlal 3 , Jean-Yves Saillard 3 , Augusto C H Da Silva 4 , Juarez L F Da Silva 4 , Thomas F Fässler 1, 2 , Roland A Fischer 1, 2
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-06-24 , DOI: 10.1021/acs.inorgchem.0c00943 Max Schütz 1, 2 , Maximilian Muhr 1, 2 , Kerstin Freitag 1 , Christian Gemel 1, 2 , Samia Kahlal 3 , Jean-Yves Saillard 3 , Augusto C H Da Silva 4 , Juarez L F Da Silva 4 , Thomas F Fässler 1, 2 , Roland A Fischer 1, 2
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Reaction of the Cu(I) sources, [Cu5](Mes)5 and [(iDipp)CuOtBu] (Mes = mesityl; iDipp = 1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene) with the Zn(I) complex [Zn2](Cp*)2 leads to a mixture of intermetallic Cu/Zn clusters with a distribution of species that is dependent on the stoichiometric ratio of the reactants, the reaction time, as well as the temperature. Systematic and careful investigation of the product mixtures rendered the isolation of two new clusters possible, i.e., the Zn-rich, red cluster 1, [CuZn10](Cp*)7 = [Cu(ZnZnCp*)3(ZnCp*)4], as well as the Cu-rich, dark-green cluster 2 [Cu10Zn2](Mes)6(Cp*)2. Structure and bonding of these two species was rationalized with the help of density functional theory calculations. Whereas 1 can be viewed as an 18-electron Cu center coordinated to four ZnCp* and three ZnZnCp* one-electron ligands (with some interligand bonding interaction), compound 2 is better to be described as a six-electron superatom cluster. This unusual electron count is associated with a prolate distortion from a spherical superatom structure. This unexpected situation is likely to be associated with the ZnCp* capping units that offer the possibility to strongly bind to the top and the bottom of the cluster in addition to the bridging mesityl ligands stabilizing the Cu core of the cluster.
中文翻译：
富铜和富锌金属间化合物Cu / Zn团簇的对比结构和键合。
Cu（I）源，[Cu 5 ]（Mes）5和[（i Dipp）CuO t Bu]（Mes =均三元醇；i Dipp = 1,3-双（2,6-二异丙基苯基）-1 H -咪唑-2-亚叉基）与Zn（I）配合物[Zn 2 ]（Cp *）2形成金属间铜/锌簇的混合物，其分布取决于反应物的化学计量比，反应时间以及温度。对产物混合物进行系统和仔细的研究后，可以分离出两个新的簇，即富锌红色簇1 [CuZn 10 ]（Cp *）7＝ [Cu（ZnZnCp *）3（ZnCp *）4 ]，以及富含铜的暗绿色簇2 [Cu 10 Zn 2 ]（Mes）6（Cp *）2。借助密度泛函理论计算，使这两个物种的结构和键合合理化。鉴于1可以看作是一个18电子的Cu中心，与四个ZnCp *和三个ZnZnCp *单电子配体（具有一些配体键相互作用）配位，所以化合物2最好被描述为六电子超原子团簇。这种异常的电子计数与球形超原子结构的扁长形畸变有关。这种意外情况很可能与ZnCp *封端单元有关，除了稳定簇的Cu核的桥连均基配体外，ZnCp *封端单元还可以牢固地结合到簇的顶部和底部。
更新日期：2020-07-06
中文翻译：
富铜和富锌金属间化合物Cu / Zn团簇的对比结构和键合。
Cu（I）源，[Cu 5 ]（Mes）5和[（i Dipp）CuO t Bu]（Mes =均三元醇；i Dipp = 1,3-双（2,6-二异丙基苯基）-1 H -咪唑-2-亚叉基）与Zn（I）配合物[Zn 2 ]（Cp *）2形成金属间铜/锌簇的混合物，其分布取决于反应物的化学计量比，反应时间以及温度。对产物混合物进行系统和仔细的研究后，可以分离出两个新的簇，即富锌红色簇1 [CuZn 10 ]（Cp *）7＝ [Cu（ZnZnCp *）3（ZnCp *）4 ]，以及富含铜的暗绿色簇2 [Cu 10 Zn 2 ]（Mes）6（Cp *）2。借助密度泛函理论计算，使这两个物种的结构和键合合理化。鉴于1可以看作是一个18电子的Cu中心，与四个ZnCp *和三个ZnZnCp *单电子配体（具有一些配体键相互作用）配位，所以化合物2最好被描述为六电子超原子团簇。这种异常的电子计数与球形超原子结构的扁长形畸变有关。这种意外情况很可能与ZnCp *封端单元有关，除了稳定簇的Cu核的桥连均基配体外，ZnCp *封端单元还可以牢固地结合到簇的顶部和底部。
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