无菌装载,已经合成了阴离子吡啶,并成功地将其用于稳定同系列硬币金属配合物。CuBr(PPh3)处理[4-(Ph3B)-2,6-Trip2Py]K(Trip=2,4,6-iPr3C6H2),AgCl(PPh3)或AuCl(PPh3)(Py=吡啶)提供相应的[4-(Ph3B)-2,6-Trip2Py]M(PPh3)(M=Au,Ag,Cu)配合物,通过盐复分解,作为隔离,结晶固体。值得注意的是,这些反应避免了用体积较小的配体系统报道的容易的单电子转移化学。X射线结构显示它们是两配位金属加合物。在三个11族家族成员中,银中的M-N和M-P键距离最长,铜加合物中的M-N和M-P键距离最短。计算分析揭示了对阴离子吡啶的空间体积的有趣的稳定性依赖性(即,硼酸吡啶基)配体。比较[4-(Ph3B)-2,6-Trip2Py]Au(PPh3)与吡啶和间三联苯配合物的结构和键合,还提供了{[2,6-Trip2Py]Au(PPh3)}[SbF6]和[2,6-Trip2Ph]Au(PPh3)。Au(I)异氰化物配合物,[4-(Ph3B)-2,6-Trip2Py]Au(CNBut)已使用相同的阴离子吡啶基硼酸盐稳定,说明其也可支持其它金配体部分。
Sterically loaded, anionic pyridine has been synthesized and utilized successfully in the stabilization of a isoleptic series of coinage metal complexes. The treatment of [4-(Ph3B)-2,6-Trip2Py]K (Trip=2,4,6-iPr3C6H2) with CuBr(PPh3), AgCl(PPh3) or AuCl(PPh3) (Py=pyridine) afforded the corresponding [4-(Ph3B)-2,6-Trip2Py]M(PPh3) (M=Au, Ag, Cu) complexes, via salt metathesis, as isolable, crystalline solids. Notably, these reactions avoid the facile single electron transfer chemistry reported with the less bulky ligand systems. The X-ray structures revealed that they are two-coordinate metal adducts. The M-N and M-P bond distances are longest in the silver and shortest in the copper adduct among the three group 11 family members. Computational analysis revealed an interesting stability dependence on steric bulk of the anionic pyridine (i. e., pyridyl borate) ligand. A comparison of structures and bonding of [4-(Ph3B)-2,6-Trip2Py]Au(PPh3) to pyridine and m-terphenyl complexes, {[2,6-Trip2Py]Au(PPh3)}[SbF6] and [2,6-Trip2Ph]Au(PPh3) are also provided. The Au(I) isocyanide complex, [4-(Ph3B)-2,6-Trip2Py]Au(CNBut) has been stabilized using the same anionic pyridylborate illustrating that it can support other gold-ligand moieties as well.