Redox and Anion Exchange Chemistry of a Stibine-Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element
Redox and Anion Exchange Chemistry of a Stibine-Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element
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DOI：
10.1002/anie.201404156
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发表时间：
2014-08-18
影响因子：
16.6
通讯作者：
Gabbai, Francois P.
中科院分区：
文献类型：
--
作者：
Jones, James S.;Wade, Casey R.;Gabbai, Francois P.
根据共价键分类（CBC）方法，双电子供体被定义为L型配体，单电子供体被定义为X型配体，而双电子受体被定义为Z型配体。这三种配体功能通常与配位原子的性质有关，膦、烷基和硼烷基团分别是L-、X-和Z-配体的原型实例。报道了一种新的SbNi平台，其中配位Sb原子可以承担所有三种CBC配体功能。使用实验和计算数据，表明PhICl 2氧化（o-（Ph 2 P）C6 H4）（3）SbNi（PPh 3）（1）为[（o-（Ph 2 P）C6 H4）（3）ClSb]-NiCl（2）伴随着1的锑化氢L型配体转化为2中的锑硼烷X型配体。此外，在环己基异氰化物存在下，2与儿茶酚二价阴离子的反应导致形成[（o-（Ph 2 P）C6 H4）（3）（o-O2 C6 H4 Sb）]Ni（CNCy）（4），其特征在于由刘易斯酸性Z型锑硼烷配体配位的镍原子的络合物。
According to the covalent bond classification (CBC) method, two-electron donors are defined as L-type ligands, one-electron donors as X-type ligands, and two-electron acceptors as Z-type ligands. These three ligand functions are usually associated to the nature of the ligating atom, with phosphine, alkyl, and borane groups being prototypical examples of L-, X- and Z-ligands, respectively. A new SbNi platform is reported in which the ligating Sb atom can assume all three CBC ligand functions. Using both experimental and computational data, it is shown that PhICl2 oxidation of (o-(Ph2P)C6H4)(3)SbNi(PPh3) (1) into [(o-(Ph2P)C6H4)(3)ClSb]-NiCl (2) is accompanied by a conversion of the stibine L-type ligand of 1 into a stiboranyl X-type ligand in 2. Furthermore, the reaction of 2 with the catecholate dianion in the presence of cyclohexyl isocyanide results in the formation of [(o-(Ph2P) C6H4)(3)(o-O2C6H4Sb)]Ni(CNCy) (4), a complex featuring a nickel atom coordinated by a Lewis acidic, Z-type, stiborane ligand.