Convergent C-H⋯[Rh]⋯H-C hydrogen-bonding.

Using a triarylphosphine functionalized at the 2-position with an acridane moiety, we have isolated a rhodium(I) complex featuring a convergent C-H⋯[Rh]⋯H-C hydrogen-bonding motif, supported in part by the two-sided involvement of the dz2 orbital with the flanking C-H antibonds. The nature of this unique motif has been established based on spectroscopic, structural, and computational grounds.