Metal-phosphido and -phosphinidene complexes in P–E bond-forming reactions

Abstract

Metal complexes bearing terminal phosphido or phosphinidene ligands have become versatile tools in the stoichiometric and catalytic preparation of phosphorus-element bonds. This Perspective describes a selection of recent advances in this field, and certain emphasis has been placed on reactions that vary from what has been previously observed. Some of the general reactivity trends and mechanistic understanding in these metal-mediated reactions that has emerged are also described. Much of what is chronicled herein comes from a flux of reports over the last decade describing unique metal-mediated phosphorus-element bond formation reactions that are likely to stimulate further discoveries.

Evidence for Iron‐Catalyzed α‐Phosphinidene Elimination with Phenylphosphine

“…The catalytic formation of main‐group bonds is of growing importance in the targeted synthesis of value‐added molecules and materials . Among the various elements, bond formation to phosphorus remains an ongoing field of study due to its increasing scarcity and importance in a variety of chemical disciplines . An acutely underdeveloped reaction in main‐group bond formation is α elimination.…”

Metal–Ligand Multiple Bonding in Thorium Phosphorus and Thorium Arsenic Complexes

“…[1][2][3][4] Phosphinidenesa nd phosphinidiides, as well as their lower congeners, arsinidenes and arsinidiides, are rare, with lesst han 50 examples in the literature. [1][2][3][4] Phosphinidenesa nd phosphinidiides, as well as their lower congeners, arsinidenes and arsinidiides, are rare, with lesst han 50 examples in the literature.…”

Deoxygenation of isocyanates via transient electrophilic terminal phosphinidene complexes: Are strained P‐heterocycles involved?

“…8 Me ( δ ( 31 P) = +18 ppm). As is the case for the free ligands, the characteristic absorptions in the IR spectrum of 12 Me and 13 Me are the exocyclic carbon-nitrogen stretching at 1842 wavenumbers (12 Me ) and the coupled exocyclic C O and cyclic C N stretching at 1936 cm −1 (13 Me ), both of which are to be observed well separated from the carbonyl stretching vibrations of the metal fragment (not given). As inferred from Kohn-Sham molecular orbital theory in the transition state, 12…”