The gas-phase reactivity of selected ionic species with borazine and of borazine-derived ions with selected neutrals has been studied by FT-ICR and ab initio computations and related to the corresponding ion chemistry of benzene. The most basic site of borazine is at nitrogen, and its conjugate acid, H3B3N3H4+, is similar in structure to the benzenium ion, as shown by ab initio calculations. H3B3N3H4+ ions undergo H/D exchange of up to four hydrogens with CD3OD and do not isomerize by stepwise 1,2-hydrogen shifts. Protonation at boron is calculated to be unfavored by 28 kcal/mol with respect to protonation at nitrogen. The H4B3N3H3+ ions show the features of a [B3N3H5-H2]+ complex, prone to dissociation at room temperature. The experimental gas-phase basicity of borazine is equal to 185.0 ( 1 kcal/mol. The Lewis basicity toward Me3Si+ places borazine into a linear correlation pertaining to model aromatic compounds. The experimental gas-phase acidity is 365.4 ( 1.5 kcal/mol. The reactions of neutral borazine with protonating, alkylating, and nitrating ions have been characterized and compared with the corresponding reactions of benzene. B3N3H5+ ions, retaining a cyclic structure, react similarly, in some respects, as phenylium ions, C6H5+.

Gas Phase Ion Chemistry of Borazine, an Inorganic Analogue of Benzene / Chiavarino, Barbara; Crestoni, Maria Elisa; DI MARZIO, Annito; Fornarini, Simonetta; M., Rosi. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 121:(1999), pp. 11204-11210. [10.1021/ja992220m]

Gas Phase Ion Chemistry of Borazine, an Inorganic Analogue of Benzene.

CHIAVARINO, Barbara;CRESTONI, Maria Elisa;DI MARZIO, Annito;FORNARINI, Simonetta;
1999

Abstract

The gas-phase reactivity of selected ionic species with borazine and of borazine-derived ions with selected neutrals has been studied by FT-ICR and ab initio computations and related to the corresponding ion chemistry of benzene. The most basic site of borazine is at nitrogen, and its conjugate acid, H3B3N3H4+, is similar in structure to the benzenium ion, as shown by ab initio calculations. H3B3N3H4+ ions undergo H/D exchange of up to four hydrogens with CD3OD and do not isomerize by stepwise 1,2-hydrogen shifts. Protonation at boron is calculated to be unfavored by 28 kcal/mol with respect to protonation at nitrogen. The H4B3N3H3+ ions show the features of a [B3N3H5-H2]+ complex, prone to dissociation at room temperature. The experimental gas-phase basicity of borazine is equal to 185.0 ( 1 kcal/mol. The Lewis basicity toward Me3Si+ places borazine into a linear correlation pertaining to model aromatic compounds. The experimental gas-phase acidity is 365.4 ( 1.5 kcal/mol. The reactions of neutral borazine with protonating, alkylating, and nitrating ions have been characterized and compared with the corresponding reactions of benzene. B3N3H5+ ions, retaining a cyclic structure, react similarly, in some respects, as phenylium ions, C6H5+.
Gas phase basicity; Protonation selectivity; Electrophilic reactions; B-N ceramics
01 Pubblicazione su rivista::01a Articolo in rivista
Gas Phase Ion Chemistry of Borazine, an Inorganic Analogue of Benzene / Chiavarino, Barbara; Crestoni, Maria Elisa; DI MARZIO, Annito; Fornarini, Simonetta; M., Rosi. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 121:(1999), pp. 11204-11210. [10.1021/ja992220m]
File allegati a questo prodotto
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/246468
 Attenzione

Attenzione! I dati visualizzati non sono stati sottoposti a validazione da parte dell'ateneo

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 54
  • ???jsp.display-item.citation.isi??? 49
social impact