Tetryl‐Tetrylene Addition to Phenylacetylene. Issue 14 (4th February 2021)

• Record Type: Journal Article
• Authors: Maudrich, Jakob‐Jonathan; Diab, Fatima; Weiß, Sebastian; Zweigart, Magda; Eichele, Klaus; Schubert, Hartmut; Müller, Robert; Kaupp, Martin; Wesemann, Lars
• Is Part Of: Chemistry. Volume 27:Issue 14(2021)
• Page Start: 4691
• Page End: 4699
• Publication Date: 2021-02-04
• Subjects: germaniumhydrides -- NMR chemical shift calculations -- stannyl cations -- tetrylenes -- tinhydrides; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202005119
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Phenylacetylene adds [Ar*GeH2 ‐SnAr'], [Ar*GeH2 ‐PbAr'] and [Ar'SnH2 ‐PbAr*] at rt in a regioselective and stereoselective reaction. The highest reactivity was found for the stannylene, which reacts immediately upon addition of one equivalent of alkyne. However, the plumbylenes exhibit addition to the alkyne only in reaction with an excess of phenylacetylene. The product of the germylplumbylene addition reacts with a second equivalent of alkyne and the product of a CH‐activation, a dimeric lead acetylide, were isolated. In the case of the stannylplumbylene the trans ‐addition product was characterized as the kinetically controlled product which isomerizes at rt to yield the cis ‐addition product, which is stabilized by an intramolecular Sn–H–Pb interaction. NMR chemical shifts of the olefins were investigated using two‐ and four‐component relativistic DFT calculations, as spin–orbit effects can be large. Hydride abstraction was carried out by treating [Ar'SnPhC=CHGeH2 Ar*] with the trityl salt [Ph3 C][Al(OC{CF3 })4 ] to yield a four membered ring cation. Abstract : Phenylacetylene adds [Ar*GeH2 ‐SnAr'], [Ar*GeH2 ‐PbAr'] and [Ar'SnH2 ‐PbAr*] in a regioselective and stereoselective reaction. NMR chemical shifts of the olefins were investigated using two‐ and four‐component relativistic DFT calculations, as spin–orbit effects can be large. Hydride abstraction was carried out by treating [Ar'SnPhC=CHGeH2 Ar*] with the trityl salt [Ph3 C][Al(OC{CF3 }3 )4 ] to yield cationic germastannacyclobutene.