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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. [ABSTRACT FROM AUTHOR]

The frustrated Lewis pair (FLP) adducts PB{ECl2} (PB = iPr2P(C6H4)BCy2; Cy = cyclohexyl; E = Si, Ge) were used to access a bis(alkynyl)-functionalized silylene and a germylene; the goal behind preparing these species was to obtain new unsaturated main group polymers [E(C≡CSiMe3)2]n upon heating. While the silylene adduct PB{Si(C≡CSiMe3)2} was stable up to 150 °C, the heavier element congener PB{Ge(C≡CSiMe3)2} underwent a complicated rearrangement process accompanied by Cy-group migration and Ge(II)-alkyne coordination. Density functional theory computations were performed to understand the mechanistic pathway for the unusual rearrangement of PB{Ge(C≡CSiMe3)2}. [ABSTRACT FROM AUTHOR]

We report phosphinidenes (PR) stabilized by an intramolecular frustrated Lewis pair (FLP) chelate. These adducts include the parent phosphinidene, PH, which is accessed via thermolysis of coordinated HPCO. The reported FLP‐PH species acts as a springboard to other phosphorus‐containing compounds, such as FLP‐adducts of diphosphorus (P2) and InP3. Our new adducts participate in thermal‐ or light‐induced phosphinidene elimination (of both PH and PR, R=organic group), transfer P2 units to an organic substrate, and yield the useful semiconductor InP at only 110 °C from solution. [ABSTRACT FROM AUTHOR]

Adducts of the parent iminoborane isomers, HBNH and NBH2, have been prepared, each stabilized by the frustrated Lewis pair (FLP) chelate iPr2P(C6H4)BCy2 (PB). PB{HBNH} was accessed via dehydrohalogenation, while the corresponding isomer PB{NBH2} was obtained from the borylation of the formal nitrene-FLP complex PB{NH}. [ABSTRACT FROM AUTHOR]