Dynamic properties of the fluxional Rh2H(μ-PPh2)2(PPh3)3−1 complex

► Diphenylphosphido-bridged dirhodium, 32 electron Rh2 complex synthesized. ► Asymmetric rhodium centers with pseudo-tetrahedral and square planar Rh centers. ► 1H and 31P NMR experiments reveal the highly dynamic structure in solution.