Intramolecular Tetrylene Lewis Adducts: Synthesis and Reactivity

• Published in: Chemistry : a European journal 2016-07, Vol.22 (28), p.9812-9826
• Main Authors: Schneider, Julia, Krebs, Kilian M., Freitag, Sarah, Eichele, Klaus, Schubert, Hartmut, Wesemann, Lars
• Format: Article
• Language: English
• Subjects: Adducts; alkyne addition; Alkynes; azides; Bonding; Chemistry; Derivatives; germylenes; Insertion; NMR spectroscopy; nucleophillic substitution; Phosphines; plumbylene; Reagents
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201601224

A series of benzyl(diphenylphosphino) and o‐phenyl(diphenlyphosphino) substituted germylenes and plumbylenes were synthesized by nucleophilic substitution between the respective lithium reagent and tetrylene halide. The Lewis pairs were characterized by X‐ray crystallography and NMR spectroscopy. The reactivity of the tetrylenes was investigated with respect to azide addition. In the germylene case, the germaniumimide was formed as the kinetically controlled product, which rearranges upon heating to give the phosphinimide. The stannylene and plumbylene derivatives react with adamantylazide to give the azide adducts. 1‐Pentene reacts diastereoselectively with the phosphagermirane to give a cyclic addition product. Trimethysilylacetylene shows an addition with the benzylphosphino‐substituted germylene and plumbylene to give the cycloheteropentene molecules. The addition product between phenylacetylene and the four membered Ge‐P adduct shows after addition at room temperature a 1,4‐phenylmigration to give a cyclic phosphine. Alkylnitrene insertion into a Ge−C bond of the alkyne addition product of the phosphagermirane was found in reaction with adamantylazide. Nucleophillic substitution: Intramolecular germylene and plumbylene adducts were synthesized, structurally characterized, and their reactivity with respect to azide and alkyne addition was studied. Pentene reacts diastereoselectively with the phosphagermirane to give a cyclic addition product. Trimethysilylacetylene shows an addition with the benzylphosphino‐substituted germylene and plumbylene to give the cycloheteropentene molecules (see scheme).