Frustrated Lewis Pair Adduct of Atomic P(−1) as a Source of Phosphinidenes (PR), Diphosphorus (P₂), and Indium Phosphide

Abstract

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 FLPadducts of diphosphorus (P 2 ) and InP 3 . Our new adducts participate in thermal-or light-induced phosphinidene elimination (of both PH and PR, R = organic group), transfer P 2 units to an organic substrate, and yield the useful semiconductor InP at only 110 °C from solution.

Atypical “Masked” Frustrated Lewis Pair Character in a Geminal‐Linked Phosphine‐Borane

“…All hydrogen atoms are omitted for clarity. Selected bond lengths [Å] and angles [°]: P1À C1 1.9015 (13), C1À B1 1.6294 (18); P1À C1À B1 117.56 (9). b) Computed HOMO (left, À 7.08 eV) and LUMO (right, À 0.42 eV) of 1, plotted with an isovalue of 0.03.…”

“…All carbon-bound hydrogen atoms are omitted for clarity. Selected bond lengths [Å] and angles [°]: P1À C1 1.8593 (18), P1À B1 1.926(2); B1À P1À C1 111.38 (9). b) Molecular structure of 5 [14] with thermal ellipsoids plotted at 50 % probability.…”

“…Recently, work in our lab has shown that the chelating FLP PB [6] (Figure 1a) forms stable adducts with group 14 (SiR 2 , GeR 2 ) and group 15 (NÀ H, PÀ R) fragments, which upon mild thermolysis or photolysis provide pathways for the solution-phase deposition of thin films of elemental Ge or Si, and polysilanes, as well as phosphinidene (PÀ R) transfer to organic substrates. [7][8][9] However, we found that the scope of phosphinidene transfer was quite limited by the high thermal and photolytic stability of the PB-phosphinidene adducts. [9,10] As a result, we sought to modify the FLP chelate bite angle to facilitate the release of main group fragments for productive materials synthesis.…”

“…[7][8][9] However, we found that the scope of phosphinidene transfer was quite limited by the high thermal and photolytic stability of the PB-phosphinidene adducts. [9,10] As a result, we sought to modify the FLP chelate bite angle to facilitate the release of main group fragments for productive materials synthesis. Our first efforts in this regard involved preparing FLP ligands with increased bite angles as compared to PB, but these proved to be much less reactive due to a strong intramolecular PÀ B bonding in their uncomplexed forms.…”

The Green Box: Selenoviologen-Based Tetracationic Cyclophane for Electrochromism, Host–Guest Interactions, and Visible-Light Photocatalysis

“…Bridging of main group elements (P, S, Se, Te, and Bi) in the bipyridine bay, as an effective modification method for viologens (V 2+ ), is developed to improve their optoelectronic properties and stabilization of cationic radical. − Among the heteroatoms-bridged viologens, selenoviologen (SeV 2+ ) has been reported as a photosensitizer as well as an electron-transfer mediator in visible-light photocatalysis, benefiting from the superior properties of its radical cations (SeV +• ). − Recently, two SeV 2+ -appendant metallacycles with highly stable radical cations and long-lived charge separation were reported, which were used for electrochromism and visible-light-induced cross-dehydrogenative coupling . It can be envisioned that introducting selenoviologens into cationic cyclophanes can not only narrow highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO–LUMO) energy gaps and improve the photophysical properties of tetracationic cyclophane but also enchance the stability of biradical dicationic species (V 2(+•) ) and retard the charge recombination of tetracationic species (V 4+ ), which are extremely essential for tetracationic cyclophane derivatives in visible-light photocatalysis.…”