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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.

The synthesis, characterization, and reactivity of a chromium(0) complex bearing an amine-borane moiety (η(6)-C(6)H(5)CH(2)NMe(2)·BH(3))Cr(CO)(3) (2) is reported. Photolysis of complex 2 results in the elimination of a CO ligand followed by the formation of an intramolecular σ-borane complex (η(1)-(η(6)-C(6)H(5)CH(2)NMe(2)·BH(2)-H))Cr(CO)(2) (3). This species was characterized in solution by NMR spectroscopy. Reaction of complex 2 with photochemically generated (OC)(5)Cr(THF) affords a novel homobimetallic σ-borane complex (OC)(3)Cr(η(6)-C(6)H(5)CH(2)NMe(2)·BH(2)-H-Cr(CO)(5)) (4), wherein one of the BH moieties is bound to the chromium center in an η(1)-fashion. The σ-borane complex 4 was isolated in moderate to good yield (72%). The BH(3) fragment in the complexes 3 and 4 are highly dynamic involving exchange of the BH hydrogen bound to the metal with the terminal BH hydrogen atoms. The dynamics has been studied using variable-temperature NMR spectroscopy. Complexes 2 and 4 have been characterized by X-ray crystallography.