Synthesis and Reactivity of Palladium- and Platinum-Bridged Heterobimetallic [3]Trochrocenophanes

Heterobimetallic [3]­trochrocenophanes with PdCl2 and
PtCl2 bridges were prepared in reasonable yields. The PdCl2 species possess, like their Pt analogues, poor solubility
but can be made more soluble by ligand substitution. By reaction of
Pd-bridged [3]­trochrocenophanes with MeLi, both Cl atoms can be substituted
by a Me group. Likewise, reaction of Pt-bridged complexes with LiCCPh
leads to the expected disubstituted compound. Herein we present the
synthesis of MCl2- and MR2-bridged (M = Pd,
Pt; R = Me, CCPh) [3]­trochrocenophanes, as well as some solid-state
structures of these [3]­trochrocenophanes.

以PdCl₂与PtCl₂作为桥联基团的异双金属[3]轮二茂铁环番（trochrocenophanes），以可观产率成功制备。该类PdCl₂桥联化合物与对应的Pt桥联衍生物类似，溶解性较差，但可通过配体取代反应提升其溶解性。通过Pd桥联的[3]轮二茂铁环番与甲基锂（MeLi）的反应，其分子中的两个氯原子均可被甲基（Me）取代。同理，Pt桥联的配合物与苯乙炔基锂（LiC≡CPh）反应后，可得到预期的二取代产物。本文报道了以MCl₂与MR₂为桥联基团（其中M为Pd、Pt；R为Me、C≡CPh）的[3]轮二茂铁环番的合成方法，以及部分该类[3]轮二茂铁环番的固态晶体结构。