Pyrolyses of the anion dihydridotetracarbonylrhenate. Crystal and molecular structure of bis(tetraethylammonium) μ-hydrido-dodecacarbonyl-triangulo-trirhenate(2-)

The pyrolyses of [NEt4][H2Re(CO)4] in boiling n-heptane, n-octane and n-nonane are described. Mixtures of polynuclear carbonyl- and hydridocarbonylrhenium species are obtained, the principal products being [Re4(CO)16]2-, [H2Re3(CO)12], [H3Re3(CO)10]2-, [H3Re3O(CO)9]2- and [H6Re4(CO)12]2-. A red-orange crystalline species was isolated from the reaction in n-heptane and shown by X-ray diffraction to be [Net4]2[HRe3(CO)12]. It gives orthorhombic crystals, space group Pbca, with cell constants a 16.07(1), b 23.39(2), c 19.49(1) Å. The structure was solved by Patterson and Fourier methods and refined by least-squares up to a final R value of 0.061, for 1303 independent counter data. The anion [HRe3(CO)12]2- contains an isosceles metal atom triangle, with two short edges of 3.014(3) and 3.018(3) Å and a long hydrogen-bridged edge of 3.125(3) Å. © 1978.