Incorporation of [Cp*Rh] and [Cp*Ir] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation
Incorporation of [Cp*Rh] and [Cp*Ir] Species into Heterobimetallic Complexes via Protonolysis Reactivity and Dioximato Chelation
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通过质子分解反应性和二肟螯合将 [Cp*Rh] 和 [Cp*Ir] 物质掺入异双金属配合物中
DOI：
10.1021/acs.inorgchem.1c01362
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发表时间：
2021
影响因子：
4.6
通讯作者：
Blakemore, James D.
中科院分区：
文献类型：
--
作者：
Kumar, Amit;Comadoll, Chelsea G.;King, Daniel S.;Oliver, Allen G.;Day, Victor W.;Blakemore, James D.
多金属化合物的合成可以使两种或两种以上金属的位置接近，但这一领域的努力往往受到试剂不相容性和缺乏选择性的阻碍。在这里，我们证明了有机金属半夹层[Cp*M] （M = Rh, Ir）片段（其中Cp*为η - 5-五甲基环戊二烯基）可以被清晰地安装到基于二亚胺-单肟-单肟配体体系的金属大环结构中。在合适的[Cp*M]物质存在下，制备了六种新的杂双金属化合物来探索这种合成化学，这种合成化学依赖于前驱体Ni（II）或Co（III）单金属配合物的原位质子分解反应。固态x射线衍射研究证实了[Cp*M]片段是通过新生二恶星位点对Rh（III）和Ir（III）中心的有效螯合而进入金属大环的。与方形平面的Ni（II）中心相比，Co（III）中心在杂双金属化合物中更倾向于八面体结构，促进醋酸酯在两种金属上的桥接连接。光谱和电化学研究揭示了金属对彼此性质的微妙影响，这与模块化化合物中M '···M距离约为3.6-3.7 Å的适中一致。综上所述，我们的结果表明，杂双金属配合物可以与有机金属[Cp*M]片段在二亚胺-二恶氧嘧啶平台上组装。
The synthesis of multimetallic compounds can enable the placement of two or more metals in close proximity, but efforts in this area are often hindered by reagent incompatibilities and a lack of selectivity. Here, we show that organometallic half-sandwich [Cp*M] (M = Rh, Ir) fragments (where Cp* is η5-pentamethylcyclopentadienyl) can be cleanly installed into metallomacrocyclic structures based on the workhorse diimine–monooxime–monooximato ligand system. Six new heterobimetallic compounds have been prepared to explore this synthetic chemistry, which relies on in situ protonolysis reactivity with precursor Ni(II) or Co(III) monometallic complexes in the presence of suitable [Cp*M] species. Solid-state X-ray diffraction studies confirm installation of the [Cp*M] fragments into the metallomacrocycles via effective chelation of the Rh(III) and Ir(III) centers by the nascent dioximato site. Contrasting with square-planar Ni(II) centers, the Co(III) centers prefer octahedral geometry in the heterobimetallic compounds, promoting bridging ligation of acetate across the two metals. Spectroscopic and electrochemical studies reveal subtle influences of the metals on each other’s properties, consistent with the moderate M′···M distances of ca. 3.6–3.7 Å in the modular compounds. Taken together, our results show that heterobimetallic complexes can be assembled with organometallic [Cp*M] fragments on the diimine–dioximato platform.