Corbo Robert, Georgiou Dayne C, Wilson David J D, Dutton Jason L
Department of Chemistry, La Trobe Institute for Molecular Science, La Trobe University , Melbourne, Victoria 3086, Australia.
Inorg Chem. 2014 Feb 3;53(3):1690-8. doi: 10.1021/ic402836d. Epub 2014 Jan 10.
The results of the reactions of the dicationic iodine(III) family of oxidants PhI(pyridine)2 with model Pd(II) and Pt(II) complexes are described. Depending on the specific reaction pairs, a variety of outcomes are observed. For palladium, Pd(IV) complexes cannot be observed but are implicated in C-C and C-N bond formation for Pd(II) starting materials based on phenylpyridine and 2,2-bipyridine, respectively. Theoretical comparisons with similar processes for -Cl and -OAc rather than pyridine indicate that these provide greater thermodynamic stability, and our results here show that they also give greater kinetic stability (the failure of MP2 methods for these systems is quite dramatic). In contrast, oxidation and delivery of the pyridine ligands gives dicationic Pt(IV) complexes that may be isolated and structurally characterized.
描述了双阳离子碘(III)类氧化剂PhI(吡啶)2与模型钯(II)和铂(II)配合物反应的结果。根据特定的反应对,观察到了多种结果。对于钯而言,无法观察到钯(IV)配合物,但基于苯基吡啶和2,2-联吡啶的钯(II)起始原料分别参与了碳-碳和碳-氮键的形成。与-Cl和-OAc而非吡啶的类似过程的理论比较表明,这些基团提供了更高的热力学稳定性,并且我们此处的结果表明它们还具有更高的动力学稳定性(MP2方法在这些体系中失效非常显著)。相比之下,吡啶配体的氧化和传递产生了可以分离并进行结构表征的双阳离子铂(IV)配合物。