RESUMO
A direct route to a doubly ferrocene bridged tetracyclic tetraphosphane 1 was developed via reductive coupling of Fe(CpPCl2)2 (2 a), where a chlorine terminated linear P4-compound 3 could be identified as an intermediate. Selective P-P bond activation was further achieved by reacting 1 with elemental selenium or [Cp*Al]4, where regioselective insertion of Se or Al atoms resulted in ferrocenylene bridged [P4Se] (4) or [P4Al] (7) moieties. Compound 7 can be transformed to a hydrogen terminated linear P4 species, 8, with protic solvents. Methylation of compound 1 with MeOTf, proceeds via intermediate formation of monomethylated species 5, which gradually produced Me2-terminated dicationic 6, again containing a linear P4-unit. Besides spectroscopic characterization, the structural details of compounds 1, 4, 6, and 8 could be determined by SC-XRD. Moreover, DFT calculations were used to rationalize the reactivity of 1, derived compounds and intermediates. As a key feature, 1 undergoes ring opening polymerization to a linear polyphosphane 9.
RESUMO
A transient phosphenium cation embedded into a [3]ferrocenophane scaffold was formed via chloride abstraction. The cation has been trapped with phosphane, carbene, and silylene donors resulting in stable adducts or bond activation of the ferrocenophane bridge. In the absence of donors, dimerization of the phosphenium cation to the corresponding dication is observed or P-C bond activation with migration of a substituent leading to a putative phosphoniodiphosphene. Using 1,3-di-tert-butylimidazol-2-silylene as the donor, further reaction of the initially formed chlorosilane leads to activation of a P-P bond of the ferrocenophane scaffold with ring expansion of the ansa-bridge. The donor formation and bonding situation are investigated by density functional theory calculations as well as experimental methods (e.g., NMR spectroscopy and X-ray crystallography).
