Heteroleptic Square Planar Cobalt(I/II) Complexes
Heteroleptic Square Planar Cobalt(I/II) Complexes
复制标题
杂配方平面钴(I/II)配合物
DOI：
10.1002/ejic.202200675
复制
发表时间：
2023
影响因子：
2.3
通讯作者：
Smith, Jeremy M.
中科院分区：
文献类型：
--
作者：
Gao, Yafei;Lee, Wei‐Tsung;Carta, Veronica;Chen, Chun‐Hsing;Telser, Joshua;Smith, Jeremy M.
钴（II）氯化配合物Ph2B(tBuIm)2Co(THF)Cl(1)在硼≡C的存在下还原得到抗磁性的方形平面钴(I)配合物Ph2B(tBuIm)2Co(C≡NtBu)2(2)。这是一个罕见的16电子钴(I)配合物的例子，它在结构上与方形平面贵金属配合物相关。因此，DFT计算的2的电子结构表明，HOMO主要是dz2in的特征。配合物2很容易被氧化成它的钴（II）同族物[Ph2B(tBuIm)2Co(C=NtBu)2]BPh4(3‐BPh4)，其EPR光谱参数具有低自旋d7的特征，在dz2亲本轨道上有一个未配对的电子。这与DFT计算的结果也是一致的。尽管它的16电子构型和HOMO的dz2亲代，唯一可处理的反应涉及一个电子氧化以提供3。
Reduction of the cobalt(II) chloride complex, Ph2B(tBuIm)2Co(THF)Cl (1) in the presence oftBuN≡C affords the diamagnetic, square planar cobalt(I) complex Ph2B(tBuIm)2Co(C≡NtBu)2(2). This is a rare example of a 16‐electron cobalt(I) complex that is structurally related to square planar noble metal complexes. Accordingly, the electronic structure of2, as calculated by DFT, reveals that the HOMO is largely dz2in character. Complex2is readily oxidized to its cobalt(II) congener [Ph2B(tBuIm)2Co(C=NtBu)2]BPh4(3‐BPh4), whose EPR spectral parameters are characteristic of low‐spin d7with an unpaired electron in an orbital of dz2parentage. This is also consistent with the results of DFT calculations. Despite its 16‐electron configuration and the dz2parentage of the HOMO, the only tractable reactions of2involve one electron oxidation to afford3.