Metalloradicals Supported by a meta‐Carborane Ligand

Abstract

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.

Metalloradicals Supported by a meta‐Carborane Ligand

“…This small energy difference is in accordance with the reversibility of the reaction observed (H atoms apart from those bound to nitrogen have been omitted for clarity). [11] Color code:Ir, dark red;O,r ed;C ,black;S ,yellow; B, grey;H ,pink;N ,blue;F,g reen. Figure 2.…”

“…Molecular structure of 5C (H atoms have been omitted for clarity). [11] Color code:I r, dark red;C ,black;S ,yellow; B, grey;N,b lue. To further explore the electronic effects of dinuclear iridium complexes,[Cp*IrCl 2 ] 2 (0.5 equiv) was reacted with 2 (Scheme 2).…”

“…Molecular structures of 6 and 7C + (H atoms have been omitted for clarity). [11] Color code:I r, dark red;S,yellow; N, blue;C, black;B ,grey;I ,orange. Angewandte Chemie Zuschriften IR.…”

Steric-Effects-Directed B–H Bond Activation of para-Carboranes

“…Carboranes are a class of carbon–boron molecular clusters with 3D aromaticity , and are finding increasing applications as useful functional building blocks in materials science, , medicine, organometallic , /coordination chemistry, and other fields. Over the past half century, the chemistry of carboranes has been greatly expanded, particularly methods for B–H bond activation and functionalization. − Among these species, o -carborane (1,2-C 2 B 10 H 12 ) is the most extensively studied example.…”

Cage–···Cage– Interaction: Boron Cluster-Based Noncovalent Bond and Its Applications in Solid-State Materials

“…Carboranes are a class of polyhedral boron–carbon molecular clusters . As one of the famous families of boron clusters, carboranes have been extensively studied because of the important applications of their derivatives in the fields of functional materials, catalysis, pharmaceuticals, etc. − For example, through tailoring the structures, carboranes can undergo efficient photo/electroluminescence, thus showing excellent performances in luminescent materials and fluorescent sensors. − In addition, carboranes as pharmacophores have also been developed for medicinal applications such as in boron neutron capture therapy (BNCT). − Despite these known important investigations, a comprehensive understanding of the structure–property relationship has not been fully established yet , because of the lack of research concerning noncovalent interactions for these polyhedral boranes.…”