Reactivity of low-oxidation state tin compounds: an overview of the benefits of combining DFT Theory and experimental NMR spectroscopy

Abstract

The reactivity and complexation properties of dicoordinated Sn(II) and Sn(0) compounds are reviewed. The (dominant) electrophilicity of the stannylenes was confirmed and quantified through density functional theory (DFT) based reactivity indices. For these compounds, combining theoretical DFT calculations and experimental nuclear magnetic resonance (NMR) spectroscopic results has evidenced their potential to undergo -complexation from aromatic clouds in addition to significantly stronger -complexation. Moreover, their potential as Lewis bases was scrutinized in their interactions and reactions with iron and tungsten carbonyl Lewis acids. Finally, a prospective comparison of the reactivity of divalent stannylenes and stannylones, with a 0 oxidation state at the Sn atom, is presented. (0) sont examinées. Le caractère électrophile (dominant) des stannylènes a été confirmé et calculé à l'aide des indices de réactivité basés sur la théorie de la fonctionnelle de la densité (DFT). Des calculs de DFT associés à des résultats expérimentaux obtenus par spectroscopie RMN ont mis en évidence que ces composés pouvaient subir, outre des très fortes -complexations, des -complexations à partir de nuages aromatiques. De plus, leur potentiel en tant que bases de Lewis a été minutieusement analysé lors de leurs interactions et réactions avec les acides de Lewis que sont le carbonyle de fer et le carbonyle de tungstène. Enfin, une comparaison éventuelle entre la réactivité des stannylènes divalents et celle des stannylones, l'atome Sn se trouvant dans un état d'oxydation 0, est présentée. [Traduit par la Rédaction] Mots-clés : composés d'étain dicoordonnés, spectroscopie RMN 119 Sn, théorie de la fonctionnelle de la densité conceptuelle, stannylènes et stannylones, réactivité. Résumé : La réactivité et les propriétés des composés dicoordonnés Sn(II) et Sn

Preface for the Special Issue dedicated to the 14th International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead (ICCOC-GTL 2013)

“…The purpose of this conference was to bring together researchers whose interests span the chemistry of germanium, tin, and lead, and this collection of manuscripts reflects the diverse range of topics presented at the conference: from the synthesis of low coordinate molecules as illustrated in the work presented by Jones 1 and studies of the reactivity of these interesting species as reported by Růžička, 2 Tokitoh 3 Willem, 4 and Baines 5 to the synthesis of high coordinate supramolecular structures as demonstrated in the work of Reuter; 6,7,8 from muon spin spectroscopy of germanium radicals as studied by West 9 to nuclear magnetic resonance spectroscopy 4 of Sn(II) and Sn(0) complexes; from the synthesis of ternary metal clusters as reported by Molloy 10 to polymers and their model oligomers as synthesized by Foucher 11 and Weinert, 12 respectively. Saito, 13 Shankar, 14 and Uhlig 15,16 describe their research on the high yielding synthesis and extended structures of several important functional tin(IV) compounds.…”