Data for Chemical Characterization of Localized Radicals in closo-Borate Anion Derivatives

lt;p style=quot;text-align:justify; margin-bottom:11pxquot;gt;lt;span style=quot;font-size:11ptquot;gt;lt;span style=quot;line-height:107%quot;gt;lt;span style=quot;font-family:Aptos,sans-serifquot;gt;lt;span arial=quot;quot; style=quot;font-family:quot;gt;The conceptual understanding of the reactivity of localized main group element radicals in molecules and ions has so far been strongly focused on carbon radicals in organic compounds. In this study, permanent anions with a radical site localized on the vacant vertex of the corresponding icosahedral lt;igt;closolt;/igt;-boranes/carboranes have been characterized by both various (radical) ion-molecule reactions in the gas phase and by computational investigations, including conceptual DFT, potential energy surfaces (PES) and energy decomposition analysis (EDA). The reactivity of these radical ions towards electron-deficient and electron-rich double bonds as well as their halogen and hydrogen atom abstraction reactions have been studied. The radical ions were varied with respect to their charge state, the nature of the spin-carrying atom and the substituents of the lt;igt;closolt;/igt;-borane scaffold. Additionally, their reactivity was compared with that of prototypical electrophilic and nucleophilic aryl radicals. lt;/spangt;lt;span arial=quot;quot; style=quot;font-family:quot;gt;Interestingly, not all the (di)anionic radicals are nucleophilic; particulary the ion [Blt;subgt;11lt;/subgt;Ilt;subgt;11lt;/subgt;C]lt;supgt;amp;bull;amp;ndash;lt;/supgt; was characterized as highly electrophilic. Hence, simple categorization based on amp;ldquo;polarity matchingamp;rdquo; arguments is not sufficient to fully explain the reactivity of these radical ions toward allyl iodide. Element-specific spatial extension of the spin density and non-covalent interactions of the allyl iodide with the lt;igt;closolt;/igt;-borane framework determine the transition state geometries and energies and therefore strongly influence the relative rate of competing reactions. These results showcase both the transferability and the limitations of amp;ldquo;classicalamp;rdquo; concepts that are typically applied successfully in Organic Chemistry for the characterization of ionic borane cluster radicals. Our approach represents a broadly applicable method for understanding the radical reactivity towards a broad range of reaction partners.lt;/spangt;lt;/spangt;lt;/spangt;lt;/spangt;lt;/pgt;

lt;p style=quot;margin-bottom:11pxquot;gt;lt;span style=quot;font-size:11ptquot;gt;lt;span style=quot;line-height:107%quot;gt;lt;span style=quot;font-family:Aptos,sans-serifquot;gt;lt;span arial=quot;quot; lang=quot;DEquot; style=quot;font-family:quot;gt;This data set includes results of tandem mass spectrometry experiments coupled with collision-activated dissociation with gas-phase ion-molecule reactions with various reagents. All mass spectrometry experiments were conducted using a Thermo Scientific LTQ linear quadrupole ion trap mass spectrometer equipped with an electrospray ionization source (ESI). All files are lt;stronggt;.csvlt;/stronggt; files named in the following order: positive or negative mode of instrument operation, source of ionization (ESI), neutral reagent, ion of interest, isolation of ion of interest and the corresponding isolation parameters. The lt;stronggt;.grflt;/stronggt; files record the change in relative abundances of the reactant and product ions as a function of time for the reactions of ions with allyl iodide. lt;/spangt;lt;/spangt;lt;/spangt;lt;/spangt;lt;/pgt;