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• W2060786880 abstract "Reactions of the binuclear complexes [{M(μ-Pz)(CNBut)2}2] (M = Rh (1), Ir (2); Pz = pyrazolate) with diiodine give the metal−metal-bonded complexes [{M(μ-Pz)(I)(CNBut)2}2] (M = Rh (3), Ir (4)). A further reaction with diiodine afford the complexes [{M(μ-Pz)(I)(CNBut)2}2(μ-I)]I, which react cleanly with CF3SO3Me replacing the ionic iodide by the triflate group. The M(I) complexes 1 and 2 are easily oxidized by mild oxidants such as [Cp2Fe]+ to give the metal−metal-bonded dications [{M(μ-Pz)(CNBut)2(MeCN)}2]2+, which add halide ions yielding the neutral complexes [{M(μ-Pz)(X)(CNBut)2}2] (M = Rh, X = Cl (7); M = Rh, Ir, X = I). These reactions indicate that the metal−metal bond formation has an electron-transfer character. Evidence of the nucleophilic attack by the metal−metal bond in complexes 3 and 4 of small molecules such as diiodine is provided by the reaction of [I(Py)2]BF4 with 7, which adds the electrophilic iodine(I) to give the bridging iodide complex [{Rh(μ-Pz)(Cl)(CNBut)2}2(μ-I)]+. In addition, an electrophile such as MeCF3SO3 abstracts one of the iodide ligands trans to the metal−metal bond in 3 to give MeI and the cationic complex [Rh2(μ-Pz)2(I)(CNBut)4]CF3SO3. This cation adds complex 3, which behaves as a metalloligand through an iodide atom, to give the tetranuclear complex [{Rh2(μ-Pz)2(I)(CNBut)4}2(μ-I)]CF3SO3 (8). The X-ray structure of 8 contains two metal−metal-bonded binuclear ‘Rh2(μ-Pz)2(I)(CNBut)4' units linked through a slightly asymmetric bridging iodine atom, showing an unusual Rh−I−Rh bond angle of 129.99(4)°. Reaction of 3 with IC⋮C−Ph gives the acetylide complex [(CNBut)2(I)Rh(μ-Pz)2(μ-I)Rh(η1-C⋮C−Ph)(CNBut)2]I. EHMO calculations on complexes [Rh2(μ-Pz)2(CNBut)4]2+, [Rh2(μ-Pz)2(I)(CNBut)4]+ [A]+, and [{Rh(μ-Pz)(I)(CNBut)2}2] successfully explain the reactivity at the metal−metal bond, that of the iodide ligand in 3 with electrophiles, and those of [A]+ with nucleophiles. Complex 3 and the cation [Rh2(μ-Pz)2(I)(CNBut)4]+ react with MeI in the presence of direct sunlight to give the oxidative-addition product [(CNBut)2(I)Rh(μ-Pz)2(μ-I)Rh(Me)(CNBut)2]+ in high yield." @default.
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• W2060786880 date "1997-10-01" @default.
• W2060786880 modified "2023-10-03" @default.
• W2060786880 title "New Perspective on the Formation and Reactivity of Metal−Metal-Bonded Dinuclear Rhodium and Iridium Complexes" @default.
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• W2060786880 doi "https://doi.org/10.1021/om970347j" @default.
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