一种非金属到金属的I-Ag配位键。
A non-metal-to-metal I-Ag coordination bond.
作者信息
Puttreddy Rakesh, Limberg Niklas, Müller Carsten, Riedel Sebastian, Frontera Antonio, Lundell Jan, Rissanen Kari
机构信息
Department of Chemistry, University of Jyvaskyla, Jyväskylä, Finland.
Department of Chemistry and Biochemistry, Freie Universität Berlin, Berlin, Germany.
出版信息
Nat Commun. 2025 Aug 13;16(1):7532. doi: 10.1038/s41467-025-62191-1.
Metal-metal bonds between metal cations are ubiquitous in coordination complexes, whereas similar bonding characteristics between non-metal and metal cations are not. Here, we report an X-ray crystal structure of a centrosymmetric complex [Ag(m-OSCF){(4MePyNO)I}] (1-AgI), where the iodine(I) cation forms an unusual 3-centre 4-electron [O-I-O] halogen bond with two oxygen atoms from two 4-methylpyridine N-oxide (4MePyNO). The iodine(I) atoms from two [4MePyNO-I-ONPyMe4] cations, which, together with the two silver(I) atoms from the paddlewheel [Ag(m-OSCF)] structure, establish two unique I-Ag bonds at 2.863(2) Å. This bond length is characteristic of bimetallic coordination bonds such as Au-Ag [2.8553(6) Å], Cu-Ag [2.8616(9) Å], and Pt-Ag [2.8602(4) Å]. Density Functional Theory calculations unambiguously support the existence of the I-Ag coordination bond between non-metal and metal cations in complex 1-AgI.
金属阳离子之间的金属-金属键在配位络合物中普遍存在，而非金属阳离子与金属阳离子之间类似的键合特征则不然。在此，我们报道了一种中心对称络合物[Ag(μ-OSCF){(4MePyNO)I}]（1-AgI）的X射线晶体结构，其中碘（I）阳离子与来自两个4-甲基吡啶N-氧化物（4MePyNO）的两个氧原子形成了一种不寻常的三中心四电子[O-I-O]卤素键。来自两个[4MePyNO-I-ONPyMe4]阳离子的碘（I）原子，与来自桨轮状[Ag(μ-OSCF)]结构的两个银（I）原子一起，在2.863(2) Å处形成了两个独特的I-Ag键。该键长是双金属配位键如Au-Ag [2.8553(6) Å]、Cu-Ag [2.8616(9) Å]和Pt-Ag [2.8602(4) Å]的特征。密度泛函理论计算明确支持了络合物1-AgI中非金属阳离子与金属阳离子之间I-Ag配位键的存在。
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