Synthesis and Reactivity of Donor‐Stabilized Bis(pentafluoroethyl)stannylene [Sn(C₂F₅)₂(D)_n] (D=THF, DMAP, PMe₃, [Sn(C₂F₅)₃]⁻)

Abstract

In this contribution we report on the synthesis of bis(pentafluoroethyl)stannane, H Sn(C F ) . In the reaction with donor molecules a ready elimination of hydrogen and the formation of the corresponding donor-stabilized monomeric bis(pentafluoroethyl)stannylene, Sn(C F ) , becomes apparent. With dependence on the Lewis basicity and steric demand of the donor, varying coordination numbers are realized. Whereas the reaction with nitrogen bases like 4-(dimethylamino)pyridine (DMAP) leads to the complexation of two donor molecules, [Sn(C F ) (dmap) ], treatment with PMe or [Sn(C F ) ] furnished the corresponding neutral or anionic monoadducts, [Sn(C F ) (D)] (D=PMe , [Sn(C F ) ] ). In contrast, the utilization of sterically demanding donors, such as iPr O, as well as the thermal treatment of ether complexes, [Sn(C F ) (D) ] (D=Et O, THF), leads to the formation of oligomeric and cyclic stannylene moieties [Sn(C F ) ] . The reactivity of H Sn(C F ) and the donor-stabilized stannylenes was proven by hydrostannylation and complexation reactions with tetracarbonylnickel and bimetallic compounds. In the latter case, a donor-dependent stannylene or distannylene insertion into the metal-metal bond was observed.

Tuning the metal–ligand bond in theσ‐complexes of stannylenes and azabenzenes

“…Heavy carbene analogues, such as stannylenes, have long been studied 1–3 and the ongoing interest in their chemistry 4–6 results from their similarities and differences to carbenes, 7 their unique reactivities 8–10 and a broad variety of their coordination patterns 11 . Stannylenes (SnX 2 ) are monomeric divalent tin species adopting a closed‐shell (singlet) ground state.…”