Rare-Earth Metal Phosphinidene Complexes: A Trip from Bridging One to Terminal One

Abstract

Conspectus As phosphorus analogues of alkylidene (or carbene) and imido (or nitrene) complexes, phosphinidene complexes have received great attention not only for their fundamental scientific merits but also for their ability to build new phosphorus-containing molecules. A large number of phosphinidene complexes in bridging, mononuclear, or terminal coordination modes have been synthesized, and their reactivity has been extensively explored. However, the synthesis of rare-earth metal (scandium, yttrium, and lanthanide metal) phosphinidene complexes lagged behind the transition metal and actinide congeners for decades. Rare-earth metal ions are among the hardest Lewis acids, whereas phosphinidene ligands are soft Lewis bases; rare-earth metal–phosphinidene coordination is thus mismatched based on the Pearson’s HSAB principle. The bridging rare-earth metal phosphinidene complexes were not reported until 2008, and the synthesis of the mononuclear and terminal species is even more challenging, which has only recently been achieved. Our group reported a bis­(μ 2-phosphinidene)­dineodymium complex in 2008. In the following >10 years, we have been pursuing the terminal rare-earth metal phosphinidene complexes. Due to the high instability of rare-earth metal–phosphorus multiple bonds, the synthesis and stabilization of these complexes are extremely difficult. Finally, by using suitable phosphinidene ligands and supporting ligands, we obtained the first mononuclear rare-earth metal phosphinidene complex in 2018 and the first terminal rare-earth metal phosphinidene complex in 2020. In these more than ten years of research, we have also found some interesting reactivity of the rare-earth metal phosphinidene complexes. The rare-earth metal bridging phosphinidene complexes can act as two-electron reductants based on the oxidative coupling of two phosphinidene ligands into a diphosphene ligand. The mononuclear rare-earth metal phosphinidene complexes catalyze the hydrogenation of terminal alkenes under mild conditions, and the joint experimental/DFT studies indicate that the hydrogenation reaction proceeds in a 1,2-addition/elimination mechanism rather than the common σ-bond metathesis mechanism. These reactivities are new and important for the rare-earth metal complexes. In addition, the ligand design in our study may contribute to the synthesis of rare-earth metal–arsenic multiple bonding complexes and alkaline-earth metal–phosphorus multiple bonding complexes, which have not yet been realized. Herein, we present an account of our investigations into rare-earth metal phosphinidene complexes, a trip from bridging one to terminal one. To give the readers an overall image of the development of the rare-earth metal phosphinidene complexes, some findings from other researchers are also included.

Panoply of P: An Array of Rhenium–Phosphorus Complexes Generated from a Transition Metal Anion

“…The ubiquitous phosphine (PR 3 ) serves as a class of ligands for many of the most historically important and industrially relevant organometallic complexes. − In addition to forming strong, covalent M–P σ-bonds, phosphines are sterically and electronically tunable, making them ideal spectator ligands for organometallic catalysts. − Metal phosphido (M–PR 2 ) and phosphinidene (MPR) complexes are also synthetically useful species, albeit for different reasons than M–PR 3 complexes. While reactivity in M–PR 3 complexes typically takes place at the metal center, reactivity in M–PR n ( n = 1, 2) complexes often directly involves the phosphorus center(s). − This makes the substituent at phosphorus, R, an even more important factor for modulating reactivity in M–PR n complexes. In general, electronegative R renders an M–PR n complex electrophilic at phosphorus, while electropositive R renders the complex nucleophilic at phosphorus. − …”