Previously, we have reported that (S)PoxIms include synand anti-conformers with respect to the N-P bonds, which can interconvert easily at room temperature via rotation of the N-phosphinoyl groups (∆E ‡ ~12 kcal mol -1 for previously reported PoxIms), even though the anticonformers are thermodynamically favorable (Figure ). Importantly, the volume and shape of the space can be drastically varied via rotation of the N-phosphinoyl groups, and a relatively limited space is present around the carbene carbon atoms in the anti-(S)PoxIms. Due to this limited spatial environment, only group-11 metals such as Cu and Au have been confirmed to form complexes that bear anti-(S)PoxIms in a -C fashion, given that these metals tend to adopt two-coordinated linear complexation geometries (Figure ). We have also reported the synthesis (IAd)Ni(CO)2 (I t Bu = 1,3-di-tert-butylimidazol-2-ylidene; IAd = 1,3-di-adamantylimidazol-2-ylidene) has already been reported which inspired us to explore the preparation of a Ni(0) complexes bearing bulky anti-(S)PoxIm ligands (Figure ).