异双金属三层配合物[(Cp*Fe)(Cp\'\'\'Co)(μ,η5:η4-P5)](1)被主族亲核试剂官能化,随后亲电猝灭或氧化。与第14族亲核试剂的反应1显示出不同的有机取代P5R中间甲板,具体取决于所用碱金属有机化合物的空间和电子效应(2:R=tBu;3:R=Me)。Further,与15组亲核试剂,第一个结构表征的与膦酰胺的单取代配合物可以作为含有环外{PR2}单元的P5配体获得(4:R=Cy,H;5:R=Ph)。分离出这些单阴离子络合物2-5,随后的亲电子猝灭揭示了新型的中性官能化多磷络合物。这些复合物带有P5R\'R\'\'的形式链(6:R\'=tBu,R\'=Me)在1,3-双置换模式或P6R\'R\'\'R\'\'\'\'\'单位(7:R\'=Cy,R\'\'=H,R\'\'\'=Me;8:R\'=Me,R\'\'=PH,R\'\'\'=Me)在1,1,3-取代中,中间甲板由一个{Cp\'\'\'Co}和一个{Cp*Fe}片段稳定。AgBF4对2、3或5的单电子氧化可以以各种配位方式获得带有P5R中间甲板的顺磁性三层配合物(R=tBu(10),R=PPh2(12))。有趣的是,对于R=Me(11),观察到二聚化,揭示了包含独特的二氢富瓦烯型P10R2配体的抗磁性四核簇。所有络合物均通过晶体学和光谱学方法(EPR,通过DFT计算阐明了多核NMR和质谱)及其电子结构。
The heterobimetallic triple-decker complex [(Cp*Fe)(Cp\'\'\'Co)(μ,η5 : η4 -P5 )] (1) was functionalized by main group nucleophiles and subsequently electrophilically quenched or oxidized. Reacting 1 with group 14 nucleophiles revealed different organo-substituted P5 R middle-decks depending on the steric and electronic effects of the used alkali metal organyls (2: R=tBu; 3: R=Me). Further, with group 15 nucleophiles, the first structural characterized monosubstituted complexes with phosphanides could be obtained as P5 ligands containing exocyclic {PR2 } units (4: R=Cy, H; 5: R=Ph). These monoanionic complexes 2-5 were isolated and subsequent electrophilic quenching revealed novel types of neutral functionalized polyphosphorus complexes. These complexes bear formal chains of P5 R\'R\'\' (6: R\'=tBu, R\'=Me) in a 1,3-disubstitution pattern or P6 R\'R\'\'R\'\'\' units (7: R\'=Cy, R\'\'=H, R\'\'\'=Me; 8: R\'=Me, R\'\'=Ph, R\'\'\'=Me) in a 1,1,3-substitution as middle-decks stabilized by one {Cp\'\'\'Co} and one {Cp*Fe} fragment. One-electron oxidation of 2, 3 or 5 by AgBF4 gave access to paramagnetic triple-decker complexes bearing P5 R middle-decks in various coordination fashions (R=tBu (10), R=PPh2 (12)). Interestingly, for R=Me (11), a dimerization is observed revealing a diamagnetic tetranuclear cluster containing a unique dihydrofulvalene-type P10 R2 ligand. All complexes were characterized by crystallographic and spectroscopic methods (EPR, multinuclear NMR and mass spectrometry) and their electronic structures were elucidated by DFT calculations.