Synthesis, characterization, and interconversion of the rhenium polyhydrides [ReH3(eta(4)-NP3)] and [ReH4(eta(4)-NP3)](+) {NP3 = tris[2-(diphenylphosphanyl)-ethyl]amine}

The rhenium(III) dichloride complex [ReCl2(eta(4)-NP3)]Cl (1) was prepared from [ReCl3(CH3CN)(PPh3)(2)] by treatment with the tripodal tetradentate ligand N(CH2CH2PPh2)(3) (NP3) in ethanol. The reaction of 1 with LiAlH4 in THF gave the rhenium(III) trihydride [ReH3(eta(4)-NP3)] (2), which was converted into the rhenium(V) tetralrydride [ReH4(eta(4)-NP3)]BPh4 (3) by protonation in CH2Cl2 with HBF4.OMe2, followed by a metathetical reaction with NaBPh4. The classical polyhydride nature of 2 and 3, as well as the overall molecular structures in solution, were determined by NMR spectroscopy, H-1 NMR relaxation, and IR spectroscopy. The polyhydride complexes 2 and 3 are stereochemically nonrigid in solution, and the thermodynamic parameters associated with the fluxional processes were determined by variable-temperature NMR studies. A single-crystal X-ray analysis of 3 has shown the complex cation [ReH4(eta(4)-NP3)](+) to be eight-coordinated by the four donor atoms of NP3 and by four terminal hydride ligands in a distorted dodecahedral geometry. An in situ IR study in CH2Cl2 has shown that the protonation of 3 occurs regioselectively at the metal center with no formation of a dihydrogen complex. Kinetic hydrogen bond products of the formula [(eta(4)-NP3)H3Re...HOR] (ROH C2H5OH, CFH2CH2OH, CF3CH2OH) were intercepted by IR spectroscopy at low temperature. The thermodynamic parameters associated with the formation of the hydrogen bond adducts were determined by either IR spectroscopy applying the logansen equation or van't Hoff plots of the formation constant vs. temperature.