A New Cubane-Type Ru4(CO)12(µ3-Se)4 Tetramer Tailored for Water Photooxidation Catalysis

Abstract

In an effort to tailor a transition metal complex for photoinduced water splitting, a new cubane-like ruthenium chalcogenide tetramer, Ru 4 (CO) 12 (µ 3 -Se) 4 , has been synthesized and structurally characterized by single-crystal X-ray diffraction. The orange-red compound crystallizes in the cubic space group I4 3m. The geometry of the Ru 4 Se 4 units remains undistorted in the cubic symmetry 3m. Such a high symmetry is exceptional among cubane-type cluster compounds. Ruthenium atoms are octahedrally coordinated by three selenium atoms and three CO groups. Ru 4 Se 4 (CO) 12 clusters are linked via van der Waals forces by oxygen atoms which belong to CO ligands of two different cluster units. By stacking of the cluster units along the cubic axes two weakly coupled three-

Surface Modified Ruthenium Nanoparticles: Structural Investigation and Surface Analysis of a Novel Catalyst for Oxygen Reduction

“…These intermediates occur during thermal decomposition using organic solutions when Ru 3 (CO) 12 reacts with dissolved selenium. Crystalline phase formation of Ru 4 Se 2 (CO) 11 was described by Layer et al Another crystalline phase we obtained as byproduct growing Ru−Se catalyst particles under equilibrium pressure in an autoclave employing xylene as solvent was cubic Ru 4 Se 4 (CO) 12 . Alonso-Vante measured a Ru:Se ratio of about 2 using Rutherford backscattering .…”

“…Crystalline phase formation of Ru 4 Se 2 (CO) 11 was described by Layer et al 26 Another crystalline phase we obtained as byproduct growing Ru-Se catalyst particles under equilibrium pressure in an autoclave employing xylene as solvent was cubic Ru 4 -Se 4 (CO) 12 . 19 Alonso-Vante measured a Ru:Se ratio of about 2 using Rutherford backscattering. 6 In our samples a Ru:Se ratio of 2.34 was inferred from TG-MS measurements.…”

“…3 Performing the process of pyrolysis in a closed vessel employing an autoclave, a cubane-type compound of composition Ru 4 Se 4 -(CO) 12 in the form of yellow orange crystallites of micrometer scale additionally appears in a black nanometer-sized ruthenium precipitate. 19 Therefore, discussing desorption experiments, where volatile constituents of an amorphous layer are released by heat treatment in an argon gas flow, the presence of this type of phase attached to the surface of the ruthenium particle surface has to be taken into account.…”

Multi-electron transfer catalysis for energy conversion based on abundant transition metals

“…Also shown is the density of states and their assignment to Ru and Se as derived from theoretical calculations. The energy gap of approximately E G is 2.4 eV appears between −0.1 and +2.3 eV [50]. the energetically favorable 4-electron transfer water oxidation reaction can be involved using a catalyst containing abundant transition metals.…”

“…A photo-catalyst for oxygen evolution, which absorbs visible light (energy gap 2.4 eV) has been theoretically calculated and synthesized in our group [50]. The metal involved was Ru, which is a metal reaching high oxidation states and which can form a peroxo complex releasing molecular oxygen.…”