Unsymmetrical sp2-sp3 Disilenes

Disilenes with differently coordinated silicon atoms are not known. Here, we have shown the high yield synthesis of a range of disilenes (2-4 and 6) upon reaction of a hypersilyl silylene PhC(NtBu)(2)SiSi(SiMe3)(3) (1) with aliphatic chlorophosphines. The most striking characteristic of these disilenes is the presence of two differently coordinated Si atoms (one is three-coordinated, the other four-coordinated). The analogous reaction with Ph2PCl did not afford the desired disilene, but, surprisingly, led to the first tetraphosphinosilane (8). DFT calculations were performed to understand the bonding in disilenes and differences in reactivity of the complexes.

Automated summary

A new synthesis method for disilenes with differently coordinated silicon atoms was demonstrated in this study. The reaction with aliphatic chlorophosphines yielded a high yield of disilenes with two differently coordinated Si atoms and even led to the formation of a new tetraphosphinosilane. DFT calculations were conducted to understand the bonding in disilenes and differences in reactivity of the complexes.