Complexes of a Frustrated Lewis Pair-Supported P(−1) Ligand

Several complexes of the intramolecular frustrated Lewis pair (FLP)-supported P(−1) ligand [ⁱPr₂P(C₆H₄)BCy₂{P}]⁻ are presented (Cy=cyclohexyl). Chief among these is the first example of a monomeric zinc bis(phosphido) complex, which was synthesized as a potential precursor for the solution-phase deposition of Zn₃P₂. While this goal was ultimately unsuccessful, the Zn(II) complex acts as a convenient springboard to other metal phosphide species via transmetallation: affording a tellurium bis(phosphido) complex and a formal adduct of the phosphorus subhalide PPCl₂. Trapping experiments show that the PPCl₂ adduct can also be prepared directly through the in situ reduction of PCl₃ in the presence of an intramolecular FLP ligand. Lastly, we report a formal η²-phosphaborene complex of cobalt(−1) which is isoelectronic to olefin complexes, and explore its bonding via density functional theory (DFT) computations.