A Nontrigonal Tricoordinate Phosphorus Ligand Exhibiting Reversible "Nonspectator" L/X-Switching.

We report here a "nonspectator" behavior for an unsupported L-function σ3 -P ligand (i.e. P{N[o-NMe-C6 H4 ]2 }, 1a) in complex with the cyclopentadienyliron dicarbonyl cation (Fp+ ). Treatment of 1a⋅Fp+ with [(Me2 N)3 S][Me3 SiF2 ] results in fluoride addition to the P-center, giving the isolable crystalline fluorometallophosphorane 1aF ⋅Fp that allows a crystallographic assessment of the variance in the Fe-P bond as a function of P-coordination number. The nonspectator reactivity of 1a⋅Fp+ is rationalized on the basis of electronic structure arguments and by comparison to trigonal analogue (Me2 N)3 P⋅Fp+ (i.e. 1b⋅Fp+ ), which is inert to fluoride addition. These observations establish a nonspectator L/X-switching in (σ3 -P)-M complexes by reversible access to higher-coordinate phosphorus ligand fragments.