A dimer of the negatively charged carbonyl cluster {Ir4(CO)11-}2 bonded by a single Ir-Ir bond, and comparison with the singly bonded (C60-)2 dimer
A dimer of the negatively charged carbonyl cluster {Ir4(CO)11-}2 bonded by a single Ir-Ir bond, and comparison with the singly bonded (C60-)2 dimer
复制标题
带负电荷的羰基簇{Ir4(CO)11-}2通过单Ir-Ir键键合的二聚体，并与单键(C60-)2二聚体的比较
DOI：
10.1002/zaac.202200368
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发表时间：
2023
影响因子：
1.4
通讯作者：
Konarev Dmitri V.
中科院分区：
文献类型：
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作者：
Sobov Pavel A.;Shestakov Alexander F.;Kuzmin Alexey V.;Khasanov Salavat S.;Otsuka Akihiro;Yamochi Hideki;Kitagawa Hiroshi;Konarev Dmitri V.
Ir 4（CO）12团簇被两当量的Cp*2Cr还原（Cp* 是η5-Me 5C 5），产生（Cp*2Cr+）2{Ir 4（CO）11−}2 4 C6 H4 Cl 2络合物。 两个Ir 4（CO）11−阴离子在阴离子{Ir 4（CO）11−} 2二聚体中通过单个Ir−Ir键结合。100 K时键长为2.8339（5）nm。 因此，簇在还原下可以形成金属-金属键合的二聚体。{Ir 4（CO）11-} 2二聚体在高达340 K甚至更高的温度下都不会解离成顺磁性物质，这表明它们具有高稳定性。 密度泛函理论计算表明，在中性或阴离子团簇中，由于失去一个CO基团，团簇可以发生二聚化。阴离子过渡金属簇的二聚化在某种程度上类似于带负电荷的碳簇-富勒烯C60 <$−的二聚化，这里我们比较两种类型的二聚体。
Reduction of the Ir4(CO)12cluster by two equivalents of Cp*2Cr (Cp* isη5‐Me5C5) produces the (Cp*2Cr+)2{Ir4(CO)11−}2⋅ 4 C6H4Cl2complex. Two Ir4(CO)11−anions are bonded by a single Ir−Ir bond in the anionic {Ir4(CO)11−}2dimer. The bond length is 2.8339(5) Å at 100 K. Therefore, clusters can form metal‐metal bonded dimers under reduction. The {Ir4(CO)11−}2dimers do not dissociate to paramagnetic species up to 340 K and even higher temperatures that indicates their high stability. DFT calculations show that dimerization of clusters can occur due to the loss of one CO group in neutral or anionic clusters. Dimerization of anionic transition metal cluster is to a certain extend similar to dimerization of negatively charged carbon cluster – fullerene C60⋅−and here we compare both types of dimers.