An intramolecular N-H ef(\u3bc-H)Re2 dihydrogen bond and a novel \u3bc3-\u3b72 coordination mode of the pyrazolate anion on a triangular cluster face

The quantitative addition of pyrazole (Hpz) to the 44 valence-electron, triangular cluster anion [Re3(\u3bc3-H)(\u3bc-H) 3(CO)9]- gives the novel unsaturated anion [Re3(\u3bc-H)4(CO)9(Hpz)]- (1, 46 valence electrons), which contains a pyrazole molecule that is terminally coordinated on a cluster vertex. Solidstate X-ray and IR analyses reveal a rather weak hydrogen-bonding interaction between the NH proton and one of the hydrides bridging the opposite triangular cluster edge (\u394H\ub0 = - 3.1 kcal.mol-1 from the Iogansen equation). Both IR and NMR data indicate that such a proton-hydride interaction is maintained in the major conformer present in CD2Cl2, but also provide evidence of the presence of minor conformers of 1 in which the NH proton is involved in an intermolecular hydrogen bond with the solvent. The \u3bc-H efHN bond length evaluated in solution through the T1 minimum value (2.07 \uc5) and that determined in the solid state by X-ray diffraction (2.05 \uc5) are in good agreement. NMR experiments show that, in acetone, intermolecular N-H ef solvent interactions replace the intramolecular dihydrogen bond. At room temperature in CH2Cl2, the pyrazole ligand in 1 is labile and 1 slowly "disproportionates" to [Re3(\u3bc3-H)(\u3bc-H) 3(CO)9]- and [Re3(\u3bc-H)3 (CO)9(\u3bc-\u3b72-pz)(Hpz)]-, with H2 evolution. Slow H2 evolution also leads to the formation of the anion [Re3(\u3bc-H)3(CO)9(pz)]- (5), in which the pyrazolate anion adopts a novel \u3bc3-\u3b72-coordination mode, as revealed by a single-crystal X-ray analysis. The analysis of the bond lengths indicates that the pyrazolate anion in 5 acts as a six-electron donor, with loss of the aromaticity. The formation of 5 from 1 is much faster in solvents with a high dielectric constant, such as acetone or DMF. Anion 5 was also obtained from the reaction of pyrazole with [Re3(\u3bc-H)3 (CO)9(\u3bc3CH3)]- through the intermediate formation of two isomeric addition derivatives and following CH4 evolution