Over the past decades, N-heterocyclic carbenes (NHCs) have been widely applied as ligands in organometallic chemistry, organocatalysts, and Lewis bases for the stabilization of reactive main group species. Multifunctional NHCs that have additional coordination sites on either the nitrogen atom(s) or on the backbone of the NHCs have led to greater diversity in the structures and functions of NHCs. Given that the utility of the multifunctional NHCs reported so far has been limited to their use as multidentate ligands for the complexation of metals, the exploration of an unprecedented application of multifunctional NHCs would significantly advance the development of their chemistry. Previously, we have proposed a concept of multifunctional multipurpose carbenes, which are carbenes that include functional groups applicable to a variety of purposes beyond solely possessing additional coordination sites. In this context, the N-phosphine-oxidesubstituted imidazolylidene, PoxIm (Figure ), and the corresponding imidazolinylidene, SPoxIm, are pioneering examples. Both molecules predominantly exist in the anti-conformation under ambient conditions, in which the carbene carbon and the phosphinoyl oxygen atoms adopt an anti-orientation with respect to the N-P bond. Rotation of the N-phosphinoyl moiety to generate the syn-conformer can occur via overcoming a relatively low energy barrier (ca. 12 kcal•mol -1 for the previously reported PoxIms). Thus, complexation between PoxIm or SPoxIm and a main-group/transition-metal element (M) can proceed in an anti--C, anti--O, syn--C, or syn--C,O fashion when an equivalent amount of PoxIm or SPoxIm and M are reacted together. Additionally, PoxIm and SPoxIm can also serve as a platform for the formation of heterobimetallic M/M′ NHC complexes via a -O-M,-C-M′ form. In this context, we have synthesized a variety of (anti--O-PoxIm)M and (anti--O-SPoxIm)M complexes using Lewis acidic compounds that tend to have high oxophilicity such as NaOTf, LiOTf, BAr3 (Ar = C6F5, p-HC6F4 ), and Al(C6F5)3. 17,18 Some of these complexes offer rare examples of complexation-induced axial chirality around the N-P bonds (Figure ). The presence of this structural motif was confirmed from the single-crystal lattice and optimized gasphase structures. This axial chirality is caused by the restricted rotation around the N-P bond due to the steric repulsion between the C5-H atom(s) of the PoxIm or SPoxIm ligand and the Lewis acid. Thus, this effect is tunable depending on the oxophilicity (which would influence the M-O distance) and size of the Lewis acid. Based on this prior work, we envisioned using a Lewis acidic rare-earth element to further explore complexation-induced N-P axial chirality.