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源自环三亚苯（一种大环三二氧戊环）的混合价自由基的铂（II）配合物。

Platinum(ii) complexes of mixed-valent radicals derived from cyclotricatechylene, a macrocyclic tris-dioxolene.

作者信息

Loughrey Jonathan J, Patmore Nathan J, Baldansuren Amgalanbaatar, Fielding Alistair J, McInnes Eric J L, Hardie Michaele J, Sproules Stephen, Halcrow Malcolm A

机构信息

School of Chemistry , University of Leeds , Woodhouse Lane , Leeds LS2 9JT , UK . Email:

Department of Chemistry , University of Sheffield , Brook Hill , Sheffield S3 7HF , UK.

出版信息

Chem Sci. 2015 Dec 1;6(12):6935-6948. doi: 10.1039/c5sc02776d. Epub 2015 Aug 20.

DOI:10.1039/c5sc02776d
PMID:29861932
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5951140/
Abstract

Three complexes of cyclotricatechylene (Hctc), [{PtL}(μ-ctc)], have been synthesised: (L = 1,2-bis(diphenylphosphino)benzene {dppb}, ; L = 1,2-bis(diphenylphosphino)ethane {dppe}, ; L = 4,4'-bis(-butyl)-2,2'-bipyridyl { Bubipy}, ). The complexes show three low-potential, chemically reversible voltammetric oxidations separated by 180 mV, corresponding to stepwise oxidation of the [ctc] catecholato rings to the semiquinonate level. The redox series and have been characterised by UV/vis/NIR spectroelectrochemistry. The mono- and di-cations have class II mixed valent character, with reduced radical delocalisation compared to an analogous bis-dioxolene system. The SOMO composition of and has been delineated by cw EPR, ENDOR and HYSCORE spectroscopies, with the aid of two monometallic model compounds [PtL(DBsq˙)] (DBsqH = 3,5-bis(-butyl)-1,2-benzosemiquinone; L = dppe or Bubipy). DF and time-dependent DF calculations confirm these interpretations, and demonstrate changes to spin-delocalisation in the ctc macrocycle as it is sequentially oxidised.

摘要

已合成了三种环三聚对苯二酚（Hctc）配合物[{PtL}(μ-ctc)]：（L = 1,2-双（二苯基膦基）苯{dppb}；L = 1,2-双（二苯基膦基）乙烷{dppe}；L = 4,4'-双（叔丁基）-2,2'-联吡啶{Bubipy}）。这些配合物显示出三个低电位、化学可逆的伏安氧化峰，峰间距为180 mV，对应于[ctc]儿茶酚环逐步氧化至半醌水平。通过紫外/可见/近红外光谱电化学对氧化还原系列 和 进行了表征。单阳离子和双阳离子具有II类混合价特征，与类似的双二氧杂环戊烯体系相比，自由基离域程度降低。借助两种单金属模型化合物[PtL(DBsq˙)]（DBsqH = 3,5-双（叔丁基）-1,2-苯半醌；L = dppe或Bubipy），通过连续波电子顺磁共振（cw EPR）、电子核双共振（ENDOR）和高分辨超精细结构（HYSCORE）光谱确定了 和 的单占据分子轨道（SOMO）组成。密度泛函（DF）和含时密度泛函（time-dependent DF）计算证实了这些解释，并证明了在环三聚对苯二酚大环顺序氧化过程中自旋离域的变化。

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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/e49e3ba8a79e/c5sc02776d-f10.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/112249e41521/c5sc02776d-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/56614801977e/c5sc02776d-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/aea8de65b617/c5sc02776d-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/e014b51bf6d6/c5sc02776d-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/9d9768563886/c5sc02776d-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/68d02e34f738/c5sc02776d-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/d5cf74138360/c5sc02776d-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/10a373955867/c5sc02776d-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/5bcc6a4ee9b6/c5sc02776d-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/51796b3ea439/c5sc02776d-f9.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b178/5951140/e49e3ba8a79e/c5sc02776d-f10.jpg

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