Alkali Metal Chlorine and Bromine Carbenoids: Their Thermal Stability and Structural Properties

The synthesis and structures of a series of M/X carbenoids of the type [Ph₂ P(S)]₂ CMX with M=Li, Na, and K and X=Cl and Br are reported, amongst the first isolated Na/Br and K/Br carbenoids. NMR spectroscopic as well as crystallographic studies showed distinct differences between the lithium carbenoids and their heavier congeners. In the solid state, all carbenoids showed no direct metal-carbon interaction, but an interaction between the metal and the halogen atom. This contact is only very weak in the case of the Li/Br carbenoid, but much more pronounced in the corresponding potassium and sodium compounds. Nevertheless, these interactions did not significantly influence the stability of the carbenoids by weakening the C-X bond and facilitating the MX elimination. As such all compounds were found to be stable up to approximately 60 °C in solution. Hence, M-X interactions-albeit being an essential feature for the structure formation of carbenoids-are not the only criterion determining the stability of such compounds. In the present systems, the stabilization by the thiophosphinoyl moieties is more important than the metal/halogen combination.