Dicationic μ‐Diborolyl Arene Triple‐Decker Complexes [CpCo(μ‐1,3‐C₃B₂Me₅)M(arene)]²⁺ (M = Rh, Ir; Cp = Cyclopentadienyl): Synthesis, Structures, Electrochemistry and Bonding

Abstract

The reaction of the bromide complexes [CpCo(μ-1,3-C 3 B 2 Me 5 )MBr 2 ] 2 [M = Rh (1), Ir (2); Cp = cyclopentadienyl] with AgBF 4 in acetonitrile affords the tris(acetonitrile (4)]. The labile nitromethane solvates [CpCo(μ-1,3-C 3 B 2 Me 5 )M(MeNO 2 ) 3 ] 2+ , generated in a similar way, react with benzene and its methylated derivatives to give the arene triple-decker complexes [CpCo(μ-1,3-C 3 B 2 Me 5 )M(arene)] 2+ [M = Rh (5), Ir (6); arene = C 6 H 6 (a), 1,2,4,5-Me 4 C 6 H 2 (b), C 6 Me 6 (c)]. The structures of 5b(BF 4 ) 2 , 5c(BF 4 ) 2 , 6b(BF 4 ) 2 and 6c(BF 4 ) 2 were determined by X-ray diffraction. The electron-transfer ability of the arene com-[a] A. N. Nesmeyanov Institute of Organoelement Compounds,

Pyridine Functionalized N-Heterocyclic Silane Complexes of Iridium and Rhodium–An Unexpected Change in Coordination

“…More precisely, reports on coordination changes of a given system without addition of extra ligands are still scarce. Thereby, reports are largely limited to hapticity changes of arene ligands after electrochemical reduction of complexes, , change of the pH and protonation or deprotonation of binding sites, , interaction with proteins or DNA, − or bond cleavage and reassembly due to altered geometry after photoisomerization of the ligand . To the best of our knowledge, there are no examples in the literature in which a distal coordination of a metal ion changes a ligand’s coordination to another reactive site.…”

Semi-differential analysis of irreversible voltammetric peaks

“…Various electrochemical processes, such as redox reactions with reduced and oxidised species present in the same phase [6,14,[21][22][23][24][25][26][27][28][29][30][31][32][33][34][35], adsorption on surfaces of electrodes [36][37][38], electrodeposition [39][40][41][42][43][44][45][46][47][48] or electrodissolution [49][50][51] were analysed by means of semi-differentiation or semi-integration. The most extensive mathematical treatment related to these methods was applied to the electrochemical reactions were both oxidised and reduced form are soluble in the electrolyte phase and their transport proceeds under conditions of semi-infinite linear diffusion [4].…”

Two-Fold C−H/C−H Cross-Coupling Using RhCl3·3H2O as the Catalyst: Direct Fusion of N-(Hetero)arylimidazolium Salts and (Hetero)arenes

“…Due to the aforementioned reasons, the Rh source to produce [Cp*RhCl 2 ] 2 , a simple inorganic salt, RhCl 3 ·3H 2 O is seldom considered as a catalyst . An easily neglected and rarely noticed fact is that neutral (hetero)­arenes are also capable of π-coordinating to Rh, although their coordination is weaker than that of anionic Cp*. We envisaged that whether RhCl 3 ·3H 2 O could be employed directly as the catalyst instead of [Cp*Rh III ] complexes for chelation-assisted C−H/C−H cross-coupling reactions considering that (hetero)­arenes could not only serve as a reaction component but also in situ π-coordinate to Rh in the reaction flask to play a similar role to Cp* ligand (Scheme b).…”