Palladium bis-pincer complexes with controlled rigidity and inter-metal distance,Inorganic Chemistry Frontiers

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Palladium bis-pincer complexes with controlled rigidity and inter-metal distance
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2020-09-22 , DOI: 10.1039/d0qi01111h
Cheng-Han Yu _{1,

2,

3,

4} , Congzhi Zhu _{1,

2,

3,

4} , Xiaozhou Ji _{1,

2,

3,

4} , Wei Hu _{1,

2,

3,

4} , Haomiao Xie _{1,

2,

3,

4} , Nattamai Bhuvanesh _{1,

2,

3,

4} , Lei Fang _{1,

2,

3,

4} , Oleg V. Ozerov _{1,

2,

3,

4}

Affiliation

We report a series of redox-active bis(pincer) Pd(II) complexes in which the redox active units are based on either a diarylamido or a carbazolide framework. Compounds 1 and 2 contain two full diarylamido/bis(pincer) PNP units connected either via an Ar–O–Ar linker (1) or an Ar–Ar bond (2). Compound 3 is a fused bis(pincer) where the two PNP units share an aromatic ring. Compound 4 is built around an indolo[3,2-b]carbazole core in which two NNN pincers share an aromatic ring similarly to 3. These metal complexes all display two reversible oxidation waves with the ΔE values increasing in the order of 1 < 2 < 4 < 3. The same trend in increasing electronic coupling emerges from the analysis of the IV-CT bands in the NIR portion of the optical spectra. The analysis of these compounds was further advanced by data from EPR spectroscopy, X-ray diffractometry, and DFT calculations. It is concluded that the monooxidized cations 2⁺–4⁺ belong to Class III on the Robin-Day classification of mixed-valence compounds. Compound 4 possesses enforced near-planarity that enables delocalization of the unpaired electron in 4⁺ across a broader conjugated system compared to 3⁺.

中文翻译：

刚性和金属间距离可控的钯双钳复合物

我们报告了一系列的氧化还原活性双（钳）Pd（II）配合物，其中氧化还原活性单元基于双芳基酰胺或咔唑骨架。化合物1和2包含两个通过Ar–O–Ar连接基（1）或Ar–Ar键（2）连接的完整的二芳基酰胺/双（钳）PNP单元。化合物3是稠合的二（钳），其中两个PNP单元共享一个芳环。化合物4是围绕吲哚[3,2- b ]咔唑核构建的，其中两个NNN钳夹与3共享一个芳环。这些金属络合物都显示出两个可逆的氧化波，ΔE值以1 < 2 < 4 < 3的顺序增加。通过分析光谱的NIR部分中的IV-CT波段，出现了增加电子耦合的相同趋势。这些化合物的分析通过EPR光谱，X射线衍射和DFT计算得到了进一步的数据。结论是，在混合价化合物的Robin-Day分类中，单氧化阳离子2 ⁺ –4 ⁺属于III类。化合物4具有强制的近平面性，与3相比，它能使4 ⁺中的未配对电子跨更宽的共轭体系离域⁺。

更新日期：2020-10-07

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