The neutral square-planar complexes Rh(acac)-(IPr)(η 2 -olefin) have been prepared from [Rh(μ-Cl)(IPr)(η 2olefin)] 2 (IPr = 1,3-bis-(2,6-diisopropylphenyl)imidazol-2-carbene; olefin = cyclooctene, ethylene) and sodium acetylacetonate (acac). Protonation of the acetylacetonato complexes with triflic acid opens the way to the formation of the putative bare [Rh-IPr] + fragment that has been stabilized at low temperature by labile ligands such as triflate, cyclooctene, and acetonitrile to generate Rh(OTf)(IPr)(η 2 -coe), [Rh(IPr)(η 2 -coe)(NCCH 3 ) 2 ]-OTf, and [Rh(IPr)(NCCH 3 ) 3 ]OTf complexes. The derivative [Rh(IPr)(η 2 -coe)(NCCH 3 ) 2 ]OTf was further characterized by an X-ray diffraction analysis.