Synthesis and structure of a dimetallated buckybowl: coordination of one [Cp*Ru]+ unit to each side of corannulene.
Synthesis and structure of a dimetallated buckybowl: coordination of one [Cp*Ru]+ unit to each side of corannulene.
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DOI：
10.1002/anie.200454225
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发表时间：
2004-08
影响因子：
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通讯作者：
P. Vecchi;C. Álvarez;A. Ellern;R. J. Angelici;A. Sygula;R. Sygula;P. W. Rabideau
中科院分区：
文献类型：
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作者：
P. Vecchi;C. Álvarez;A. Ellern;R. J. Angelici;A. Sygula;R. Sygula;P. W. Rabideau
在巴克敏斯特富勒烯（C60）的过渡金属配合物中，[1]金属原子与两个六元环共享的两个碳原子（η2）键合。另一方面，曲面碎片的C60，称为巴基碗，是很难制备和过渡金属配合物的报道很少。[2-4]合成corannulene [5，6]（C20 H10，1）的改进方法导致制备了η6配合物[Cp* Ru（η6-C20 H10）]（O3 SCF 3）[3]和[Cp* Ir（η6-C20 H10）]（BF 4）2，[4]，其中Cp* 是η5-C5 Me 5。虽然这些配合物已经通过它们的NMR光谱进行了很好的表征，但是它们都没有被分离为分析纯的固体。近年来，气相沉积法合成了[{Rh 2（O2 CCF 3）4} m·（C20 H10）n]（m：n= 1：1和3：2）。[2a]通过X射线衍射研究确定了它们的结构，它们含有[Rh 2（O2 CCF 3）4]和corannulene单元的一维和二维网络，其中{Rh 2}基团与corannulene的凸侧和凹侧都有η2-配位。这些是corannulene过渡金属配合物的唯一晶体结构。在这里，我们报告的第一个X-射线结构表征的corannulene含有η6-协调的金属片段。特别令人感兴趣的是观察到两个{Cp * Ru}+碎片位于corannulene碗的相对两侧，与游离corannulene相比，其明显变平。（0.020 mmol）与AgBF 4（对于2a）或AgPF 6（2b）（0.081 mmol）和1（0.040 mmol）在2：在室温下，在Ar气氛下，在CD_3 NO_2中，{Cp* Ru}~+与C_（20）H_（10）之比为1，得到双金属配合物[（Cp* Ru）_2（μ2-η6，η6-C20H10）] X2（X= BF 4 η（2a），PF 6 η（2b））（图1）。2a和2b都是
In transition-metal complexes of buckminsterfullerene (C60),[1] the metal atom is bonded to two carbon atoms (η2) shared by two six-membered rings. On the other hand, curved-surface fragments of C60, called buckybowls, are difficult to prepare and few transition-metal complexes of them have been reported.[2–4] Improved procedures for the synthesis of corannulene [5, 6](C20H10, 1) have led to the preparation of the η6 complexes[Cp* Ru (η6-C20H10)](O3SCF3)[3] and [Cp* Ir (η6-C20H10)](BF4) 2,[4] in which Cp* is η5-C5Me5. Although these complexes have been wellcharacterized by their NMR spectra, neither has been isolated as the analytically pure solid. Recently, the gas-phase deposition synthesis of [{Rh2 (O2CCF3) 4} m·(C20H10) n](m: n= 1: 1 and 3: 2), were reported.[2a] Their structures, as determined by X-ray diffraction studies, contain 1D and 2D networks of [Rh2 (O2CCF3) 4] and corannulene units in which the {Rh2} groups are η2-coordinated to both the convex and concave sides of the corannulene. These are the only crystal structures of transition-metal complexes of corannulene. Herein, we report the first X-ray structural characterization of a corannulene that contains η6-coordinated metal fragments. Of particular interest are the observations that the two {Cp* Ru}+ fragments are on opposite sides of the corannulene bowl, which is significantly flattened as compared to free corannulene.The reaction of [{Cp* Ru (μ3-Cl)} 4][7](0.020 mmol) with AgBF4 (for 2a) or AgPF6(2b)(0.081 mmol) and 1 (0.040 mmol) in a 2: 1 ratio of {Cp* Ru}+ to C20H10 in CD3NO2 under an Ar atmosphere at room temperature gave the dimetallated complex [(Cp* Ru) 2 (μ2-η6, η6-C20H10)] X2 (X= BF4 À (2a), PF6 À (2b))(Figure 1). Both 2a and 2b are