Metal‐only Lewis Pairs of Rhodium with s, p and d‐Block Metals

Metal‐only Lewis pairs (MOLPs) in which the two metal fragments are solely connected by a dative M→M bond represent privileged architectures to acquire fundamental understanding of bimetallic bonding. This has important implications in many catalytic processes or supramolecular systems that rely on synergistic effects between two metals. However, a systematic experimental/computational approach on a well‐defined class of compounds is lacking. Here we report a family of MOLPs constructed around the Rh(I) precursor [(η (5)‐C(5)Me(5))Rh(PMe(3))(2)] (1) with a series of s, p and d‐block metals, mostly from the main group elements, and investigate their bonding by computational means. Among the new MOLPs, we have structurally characterized those formed by dative bonding between 1 and MgMeBr, AlMe(3), GeCl(2), SnCl(2), ZnMe(2) and Zn(C(6)F(5))(2,) as well as spectroscopically identified the ones resulting from coordination to MBAr(F) (M=Na, Li; BAr(F) (−)=[B(C(6)H(2)‐3,5‐(CF(3))(2))(4)](−)) and CuCl. Some of these compounds represent unique examples of bimetallic structures, such as the first unambiguous cases of Rh→Mg dative bonding or base‐free rhodium bound germylene and stannylene species. Multinuclear NMR spectroscopy, including (103)Rh NMR, is used to probe the formation of Rh→M bonds. A comprehensive theoretical analysis of those provides clear trends. As anticipated, greater bond covalency is found for the more electronegative acids, whereas ionic character dominates for the least electronegative nuclei, though some degree of electron sharing is identified in all cases.