Polynuclear metal carbonyl hydrides of manganese, ruthenium, and osmium

Hydrogen Generation from Formic Acid Decomposition by Ruthenium Carbonyl Complexes. Tetraruthenium Dodecacarbonyl Tetrahydride as an Active Intermediate

“…Various approaches [41][42][43][44][45] have been reported for the synthesis of 12, including the treatment of [Ru 3 (CO) 12 ] with different hydride sources such as sodium borohydride or sodium amalgam, [43] high-pressure reductive carbonylation of chloro-ruthenium(II) carbonyl complexes, [41] and the hydrogenation of [Ru 3 (CO) 12 ] with hydrogen gas at atmospheric [44] or high pressures (2175 psi). [45] However, to the best of our knowledge this is the first example for the preparation of [Ru 4 (CO) 12 H 4 ] directly from RuCl 3 using FA as the exclusive source of carbonyl and hydride ligands.…”

Energy-dependent Electrospray Ionisation Mass Spectrometry of Carbonyl Clusters

“…However, these fears proved largely unfounded and early experiments on simple binary carbonyl clusters [4,5] were soon followed by studies of larger clusters [6]. Despite difficulties with carbonyl hydride clusters due to complications arising from the loss of both H and CO groups [7], mass spectrometry was shown to be a useful tool for elucidating the correct stoichiometry of such compounds [8]. One advantage in the study of neutral metal carbonyl clusters is their reasonably high volatility.…”

Edge‐Bridging and Face‐Bridging Hydrogen Atoms in Trinuclear Rhenium Carbonyl Hydrides

“…Loss of a carbonyl group from this H 3 Re 3 (CO) 11 structure with concurrent conversion of one of the edge-bridging hydrogen atoms to a face-bridging hydrogen atom gives the lowest energy H 3 Re 3 (CO) 10 structure. Further loss of a carbonyl group from this (μ 3 -H)(μ-H) 2 Re 3 (CO) 10 structure with concurrent conversion of a second edge-bridging hydrogen atom to a facebridging hydrogen atom leads to the lowest energy H 3 Re 3 (CO) 9 structure. This (μ 3 -H) 2 (μ-H)Re 3 (CO) 9 structure with a central Re 3 (μ 3 -H) 2 trigonal bipyramid appears to be a very favorable structure since it not only is the lowest energy H 3 Re 3 (CO) 9 structure but lies more than 22 kcal/mol below the next lowest energy H 3 Re 3 (CO) 9 structure.…”

“…Structures were found with the Re-Re edges of these triangles bridged by either one or two hydrogen atoms as well as structures with hydrogen atoms bridging the entire Re 3 triangle. The lowest energy H 3 Re 3 (CO) 9 structure with a central Re 3 (μ 3 -H) 2 trigonal bipyramid is of particular interest. Related structures exist for H 3 Mn 3 (CO) n (n = 12, 11, 10, 9), [18] however, the rhenium analogues are found experimentally to be significantly more stable.…”

“…[8] In addition, the manganese analogue H 3 Mn 3 (CO) 12 was synthesized by Johnson and Lewis by the reaction of Mn 2 (CO) 10 with a base followed by acidification. [9,10] The trinuclear metal carbonyl hydrides H 3 M 3 (CO) 12 (M = Mn, Tc, Re) form a series of stable compounds that are isoelectronic with the homoleptic trinuclear metal carbonyls MЈ 3 (CO) 12 (M = Fe, Ru, Os), all of which are also stable compounds. The structures of the homoleptic trinuclear metal carbonyls are of interest since Fe 3 (CO) 12 has a doubly bridged structure (Dahl [11] and Cotton [12] ), whereas M 3 -(CO) 12 (M = Ru, [13] Os, [14,15] ) have unbridged structures (Figure 1).…”