NHC-stabilized 2-hydrophosphasilenes are obtained from 1,2-dihydro-2-chlorophosphasilanes as Si(IV) precursors by a NHC-assisted 1,2-elimination of HCl. The NHC-exchange of these compounds is demonstrated as a proof of donor acceptor bonding between NHC and the silicon centre of the “SiP” moiety. We have also explored the possibility of similar exchanges in NHC-stabilized Si₂ and P₂ compounds. Theoretical DFT calculations were performed to address the nature of Si–P bonding in the NHC-stabilized 2-hydrophosphasilenes.