Silicon Tris(perchloro)dioxolene: A Neutral Triplet Diradical

Abstract

The reaction of ortho-quinones with silicon tetraiodide leads to neutral silicon trisdioxolenes in high yield, delivering the unknown oxidized form of triscatecholatosilicate dianions and the first example of open-shell semiquinonates connected via as ingle non-metal center.S ilicon tris(perchloro)dioxolene is as table diradical with at riplet ground state,a s supported by X-raydiffraction;IR, resonance Raman, UV/Vis, and (VT)EPR spectroscopy; and Kohn-Sham broken-symmetry computations.P reliminary results suggest that the preferred magnetic ground state can be altered through variation of the substituents.

The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si–O Bond

“…More recently, pentacoordinate catecholato silicates were showcased as alkyl radical precursors in photoredox catalytic applications . The redox active nature of catecholates in the coordination sphere of silicon enabled stable triplet diradicals and powerful organic oxidants . Moreover, catecholato silicates were used as building blocks for the first silicon-organic frameworks .…”

“…4 The redox active nature of catecholates in the coordination sphere of silicon enabled stable triplet diradicals and powerful organic oxidants. 5 Moreover, catecholato silicates were used as building blocks for the first silicon-organic frameworks. 6 Hence, a wealth of knowledge exists on the hypercoordinate adducts of bis-(catecholato)silanes − but the very same is missing for the parent tetracoordinated precursors, Si(cat X ) 2 (cat X = o-O 2 C 6 X 4 ).…”

Bis(catecholato)silicates: Synthesis and Structural Data

“…Bis(catecholato)silane indeed exists only in solution as an insoluble oligomer [6] . Of note, the tris(catecholato)silicate dianion has also been described but despite a recent highly interesting report by Greb [7a] its chemistry has so far been limited in terms of applications (Figure 2).…”

Synthesis, Structure and Electrochemical Properties of Acetamide- and Caprolactam-Containing Silicon Catecholates

“…Silicon complexes with tetrahalogen-substituted catecholate ligands possess catalytic activity in the reactions of aldehyde hydrosilylation [3] related to the high Lewis acidity of Si(Cat) 2 fragments that exceed the acidity of SbF 5 [4,5]. Halogensubstituted catecholate anions are even able to stabilize a triplet state of silicon [6], which allows stable Si(Cat) 2 radical to be obtained, with spin density distributed over the ligands. Some other substituted catecholates were used for the construction of macrocyclic and framework assemblies with large pores [1,2,[7][8][9][10].…”