Scorpionate ligands provide the benefit of hemilability while minimizing complete dissociation of the ligand. Previous investigations into Tp′PtL_nX_m complexes [Tp′ = hydridotris(3,5-dimethylpyrazolyl)borate] revealed the importance of hemilability as the Tp′ ligand facilitates Pt(II/IV) interconversions. Here we discuss the synthesis and metalation of a series of asymmetric scorpionate ligands bearing two pyrazolyl rings and one triazolyl ring. In addition to utilizing triazole donor arms with differing substituents, we also compare octahedral structures of Pt(IV) complexes with P = O and CH and BH caps at the pole of the facial tridentate umbrella. Oxidation from Pt(II) to Pt(IV) with electrophilic reagents, simple acids and acid chlorides, leads to isomers in some cases, and the binding properties of the various donor arms dictate the stereochemistry of the products. Investigations into the reactivity of heteroscorpionate tridentate ligands bound to platinum(II) led to CCl activation reactions with methylene chloride and 1,2-dichloroethane. Isolation of a dinuclear platinum complex bridged by an ethylene unit produced an unusual proton NMR AA′XX′ pattern in the ¹H NMR spectrum due to chirality at each platinum center.

蝎形配体提供了半合性的好处，同时使配体的完全解离最小。先前对Tp'PtL _n X _m复合物[Tp'=氢化三（3,5-二甲基吡唑基）硼酸酯]的研究表明，由于Tp'配体有助于Pt（II / IV）相互转化，因此具有半程性的重要性。在这里，我们讨论了一系列带有两个吡唑基环和一个三唑基环的不对称蝎形配体的合成和金属化。除了利用具有不同取代基的三唑供体臂之外，我们还比较了Pt（IV）配合物的八面体结构，其中P = O，CH和BH形帽位于面部三齿雨伞的撑杆处。用亲电子试剂，简单的酸和酰氯从Pt（II）氧化为Pt（IV），在某些情况下会导致异构体，并且各种供体臂的结合特性决定了产物的立体化学。对与铂（II）结合的异蝎子三齿配体的反应性的研究导致了与二氯甲烷和1,2-二氯乙烷的C Cl活化反应。由于每个铂中心的手性，分离出一个由乙烯单元桥接的双核铂配合物会在¹ H NMR光谱中产生不同寻常的质子NMR AA'XX'模式。