Synthesis and characterization of cis,trans-[RuH(η(2)-H2)(PPh3)2(N-N)][OTf] (N-N = 2,2'-bipyridyl (bpy) 1a, 2,2'-bipyrimidine (bpm) 2a; OTf = trifluoromethane sulfonate (CF3SO3)) complexes are reported. The cis-H2/hydride ligands are involved in H-atom site exchange between the two moieties. This dynamics was investigated by variable temperature NMR spectral studies based on which the mechanism of the exchange process was deduced. The ΔG(≠) for the exchange of H-atoms between the η(2)-H2 and hydride ligands was determined to be around 8 and 13 kJ mol(-1), respectively, for 1a and 2a. The H-H distances (d(HH), Å) in complexes 1a and 2a have been calculated from the T1(minimum) and (1)J(H,D) and are found to be 1.07 Å (slow) and 0.95 Å for 1a and 1.04 Å (slow) and 0.94 Å for 2a, respectively. The molecular structure of 1a was determined by X-ray crystallography.
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