Metalloradicals Supported by a meta‐Carborane Ligand

In this work, a pincer‐type complex [Cp*Ir‐(SNPh)(SNHPh)(C2B10H9)] (2) was synthesized and its reactivity studied in detail. Interestingly, molecular hydrogen can induce the transformation between the metalloradical [Cp*Ir‐(SNPh)2(C2B10H9)] (5.) and 2. A mixed‐valence complex, [(Cp*Ir)2‐(SNPh)2(C2B1...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-06, Vol.58 (24), p.8129-8133
Main Authors: Cui, Peng‐Fei, Gao, Yang, Guo, Shu‐Ting, Lin, Yue‐Jian, Li, Zhen‐Hua, Jin, Guo‐Xin
Format: Article
Language:English
Subjects:
boron
Carborane
carboranes
iridium
metalloradicals
Oxidation
structure elucidation
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Summary:In this work, a pincer‐type complex [Cp*Ir‐(SNPh)(SNHPh)(C2B10H9)] (2) was synthesized and its reactivity studied in detail. Interestingly, molecular hydrogen can induce the transformation between the metalloradical [Cp*Ir‐(SNPh)2(C2B10H9)] (5.) and 2. A mixed‐valence complex, [(Cp*Ir)2‐(SNPh)2(C2B10H8)] (7.+), was also synthesized by one‐electron oxidation. Studies show that 7.+ is fully delocalized, possessing a four‐centered‐one‐electron (S‐Ir‐Ir‐S) bonding interaction. DFT calculations were also in good agreement with the experimental results. Metal to metal: The metalloradical species [(Cp*Ir)2‐(SNPh)2(C2B10H8)] and [Cp*Ir‐(SNPh)2(C2B10H9)], based on carborane backbone ligands, have been synthesized by oxidation with I2 and loss of H2, respectively. Evidence indicates that the mixed‐valence [(Cp*Ir)2‐(SNPh)2(C2B10H8)] is fully delocalized, possessing a four‐centered‐one‐electron (S‐Ir‐Ir‐S) bonding interaction. Interestingly, molecular hydrogen can induce the reverse transformation of the neutral radical [Cp*Ir‐(SNPh)2(C2B10H9)].
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201903467