Redox and Anion Exchange Chemistry of a Stibine-Nickel Complex: Writing the L, X, Z Ligand Alphabet with a Single Element
作者:James S. Jones、Casey R. Wade、François P. Gabbaï
DOI:10.1002/anie.201404156
日期:2014.8.18
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
根据共价键分类(CBC)方法,将两个电子供体定义为L型配体,将一个电子供体定义为X型配体,将两个电子受体定义为Z型配体。这三个配体功能通常与连接原子的性质有关,其中膦,烷基和硼烷基团分别是L-,X-和Z-配体的典型例子。据报道,在一个新的SbNi平台中,连接的Sb原子可以承担所有三个CBC配体的功能。使用实验和计算数据,都表明(o-(Ph 2 P)C 6 H 4)3 SbNi(PPh 3)(1)的PhICl 2氧化为[(o- (PH 2 P)C ^ 6 ħ 4)3 ClSb]的NiCl(2)伴随着转化的锑化氢L型配体的1成在stiboranyl X型配体2。此外,在环己基异氰化物的存在下2与儿茶酚酸二阴离子的反应导致[[ o-(Ph 2 P)C 6 H 4)3(o- O 2 C 6 H 4 Sb)] Ni( CNCy)(4)的络合物,其特征是镍原子由路易斯酸性Z型斯蒂硼烷配体配位。