Synthesis and chemical characterization of the new anions [Rh₃(µ₃-E)₂(CO)₆]^–(E = S or Se). Crystal and molecular structures of [PPh₄][Rh₃(µ₃-S)₂(CO)₆] and [NMe₄][Rh₃(µ₃-Se)₂(CO)₆]

Deprotonation of Cp2Ti(SH)2 with Mononuclear Rhodium and Iridium Compounds: A New Route to Trinuclear Early−Late Heterobimetallic Complexes

“…In 8 , the three Ir···Ir separations are statistically different, spread out between 3.0435(14) and 3.1198(11) Å, and reducing consequently to C s , the symmetry of this anion in the solid state. As reported by Garlaschelli et al in [NMe 3 (CH 2 Ph)][Ir 3 (μ 3 -S) 2 (CO) 6 ],25a these intermetallic separations are clearly longer if compared with metal−metal bond distances observed in tetra- or hexanuclear iridium carbonyl complexes (2.65−2.80 Å), but are short enough to be indicative of weak intermetallic interactions. , On the other hand, all the remaining Ir−S (mean 2.364(2) Å), Ir−C (mean 1.848(5) Å), and C−O (mean 1.143(5) Å) bond distances are identical and compare well with values reported previously.…”

“…Each iridium center displays a square-planar geometry by coordination to two cis μ 3 -bridging sulfidos and two terminal carbonyl groups. The structure of this anionic complex has been previously reported forming part of the ionic compound [NMe 3 (CH 2 Ph)][Ir 3 (μ 3 -S) 2 (CO) 6 ];25a in this salt, two structurally different trinuclear anions were found in the asymmetric unit: one anion with idealized D 3 h symmetry (Ir···Ir 3.084−3.088(1) Å) and the second one in which the symmetry is lowered to C 2 v due to the shortening of two Ir···Ir distances (3.064 and 3.065(1) Å) and the lengthening of the remaining one (3.127(1) Å). In 8 , the three Ir···Ir separations are statistically different, spread out between 3.0435(14) and 3.1198(11) Å, and reducing consequently to C s , the symmetry of this anion in the solid state.…”

“…The anions [M 3 (μ 3 -S) 2 (CO) 6 ] - (M = Rh and Ir) have been previously obtained by several methods and structurally characterized by Garlaschelli et al The degradation of the clusters [M 4 (CO) 12 ] and [M 6 (CO) 16 ] with KSCN and potassium polysulfide and the reaction of the anionic complexes [MCl 2 (CO) 2 ] - (M = Rh, Ir) with [N(PPh 3 ) 2 ] 2 S give both anions in yields ranging from 60 to 80%. [Cp 2 Ti(acac)]ClO 4 was prepared by reaction of Cp 2 TiCl 2 with AgClO 4 in water in the presence of acetylacetone, probably via the intermediate species [Cp 2 Ti(OH)] + ; however, a crystal structure of compounds containing this cation has not been reported yet.…”

Ethanol Synthesis from Carbon Dioxide on [Rh10Se]/TiO2Catalyst Characterized by X-Ray Absorption Fine Structure Spectroscopy

“…The supported cluster was prepared from [ (11,12). The TiO 2 (P25), Al 2 O 3 (alon C), and SiO 2 (Davison 952) were treated at 573 K under vacuum for 2 h prior to use as supports.…”

Selenium-doped hexarhodium carbonyl clusters on magnesia: structures and promoting effects in ethene hydroformylation

“…Metal clusters have often been used as precursors of supported metal catalysts. The most prevailing advantage for using metal clusters is to prepare dispersed, fine metal particles on inorganic (d) n-8 (e) n« 13 Experimental Section…”