NEW PERSPECTIVE ON THE FORMATION AND REACTIVITY OF METAL-METAL-BONDED DINUCLEAR RHODIUM AND IRIDIUM COMPLEXES
NEW PERSPECTIVE ON THE FORMATION AND REACTIVITY OF METAL-METAL-BONDED DINUCLEAR RHODIUM AND IRIDIUM COMPLEXES
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金属-金属键合双核铑和铱配合物的形成和反应性的新视角
DOI：
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发表时间：
1997
期刊：
影响因子：
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通讯作者：
L. Oro
中科院分区：
文献类型：
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作者：
C. Tejel;M. Ciriano;José A López;F. Lahoz;L. Oro
双核配合物[{M（μ-Pz）（CNBut）2}2]（M = Rh（1），Ir（2; Pz =吡唑盐）与二碘反应得到金属-金属键合配合物[{M（μ-Pz）（I）（CNBut）2}2]（M = Rh（3），Ir（4））。进一步与二碘反应得到配合物[{M（μ-Pz）（I）（CNBut）2}2（μ-I）]I，该配合物与CF_3SO_3Me反应生成三氟甲磺酸酯基取代碘离子。M（I）配合物1和2很容易被温和的氧化剂如[Cp 2Fe]+氧化，得到金属-金属键合的二价阳离子[{M（μ-Pz）（CNBut）2（MeCN）}2]2+，其加入卤素离子，得到中性配合物[{M（μ-Pz）（X）（CNBut）2}2]（M = Rh，X = Cl（7）; M = Rh，Ir，X = I）。这些反应表明，金属-金属键的形成具有电子转移特性。[I（Py）2] BF 4与7的反应提供了小分子如二碘的配合物3和4中金属-金属键亲核攻击的证据，该反应加入亲电碘（I），得到桥联碘配合物[{Rh（μ-Pz）（Cl）（CNBut）2}2（μ-I）]+。此外，一个…
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, a...