The mixed-metal carbonyl cluster anion [Os3Ir(CO)13]−: synthesis, structure, reactivity and catalytic activity in the carbonylation of methanol

Iridium–Ruthenium–gold cluster complexes: Structures, and skeletal Rearrangements

“…[4]. Iridiumeruthenium complexes have been shown to serve as precursors to catalysts for the carbonylation methanol [5]. Supported bimetallic iridiumeruthenium catalysts have been shown to produce C 2 oxygenates from syngas [6] and also to exhibit unusually high catalytic activity for the oxygen evolution reaction in the electrolysis of water [7].…”

“…If one considers compound 3 as a IrRu 3 An ORTEP diagram of the molecular structure of HIrRu 3 (CO)12 (AuPPh 3 ) 2 , 2 showing 20% thermal ellipsoid probabilities. Selected interatomic bond distances (Å) and angles (o) are as follows: Au(1)eAu(2) ¼ 2.8563(10), Au(1)eIr(1) ¼ 2.7769(10), Au(1)e Ru(2) ¼ 3.0746(16), Au(1)eRu(3) ¼ 2.8049(15), Au(2)eIr(1) ¼ 2.7908(10), Au(2)e Ru(3) ¼ 2.8555(16), Ir(1)eRu(1) ¼ 2.7597(17), Ir(1)eRu(2) ¼ 2.7915(16), Ir(1)e Ru(3) ¼ 2.9606(16), Ru(1)eRu(2) ¼ 2.992(2), Ru(1)eRu(3) ¼ 2.749(2), Ru(2)e Ru(3) ¼ 2.9621(19); Au(1)eIr(1)eRu(1) ¼ 111.91(4), Au(1)eRu(2)eRu(1) ¼ 98.25(5), Au(1)eRu(3)eRu(1) ¼ 111.38(6), Au(1)eAu(2)eRu(3) ¼ 58.82(3), Au(1)eAu(2)e Ir(1) ¼ 58.90(3), Au(2)eAu(1)eRu(2) ¼ 105.67(4), Au(2)eIr(1)eRu(1) ¼ 101.18(4), Au(2)e Ir(1)eRu(2) ¼ 115.77(4), Au(2)eRu(3)eRu(1) ¼ 99.84(6), Au(2)eRu(3)eRu(2) ¼ 108.72(5).…”

The ligand polyhedral model: its application to carbonyl clusters containing thirteen carbonyl groups†

“…The notable exception to the capped-icosahedral geometry of the CO envelope in [M 4 (CO) 13 ] nϪ is [M 3 Ir(CO) 13 ] Ϫ (Fig. 4(a), M = Os, 12 and Fig. 4(b), Ru, 9 in isomer B), in which a cubeoctahedral based geometry is observed.…”

Fixation and spontaneous dehydrogenation of methanol on a triruthenium–iridium framework: synthesis and structure of the cluster anion [HRu3Ir(CO)12(OMe)]−

“…2 Recently we reported a series of Ru 3 Ir and Os 3 Ir mixed-metal clusters which show reasonable catalytic activity in the carbonylation of methanol to give acetic acid. 3,4 The cluster anions [Ru 3 Ir(CO) 13 ] 2 1 and [Os 3 Ir(CO) 13 ] 2 4, used as catalyst precursors in this process, are however unstable under the reaction conditions, which has been confirmed by the isolation of the fragmentation products Ir 4 (CO) 12 and [N(PPh 3 ) 2 ][M(CO) 3 I 3 ] (M = Ru, Os). 4 In this context we were interested in the behaviour of these anionic clusters towards reagents participating in the catalytic process, especially in the reaction with methanol.…”