Tetryl‐Tetrylene Addition to Phenylacetylene

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=CHGeH2Ar*] with the trityl salt [Ph3C][Al(OC{CF3})4] to yield a four membered ring cation.

Molecular Main Group Metal Hydrides

“…1113 Ar Me6 SnH 2 −PbAr iPr6 (1116) interacts with excess phenylacetylene to yield red crystals of the trans 1,2insertion product [Ar Me6 SnH 2 −C(Ph)=C(H)-PbAr iPr6 ] (1117) (eq 89). 1215…”

“…1270 Monosilylated arsenide anions have also been prepared with various counterions. For example, Westerhausen showed that the calcium bis-amide Ca[N(SiMe 3 ) 2 ] 2 was able to deprotonate the silylated primary arsine H 2 As−Si i Pr 3 (1215) generating a new calcium bis(silyl)arsenide [Ca(THF) 4 {AsH-(Si i Pr 3 )} 2 ] (1216, eq 103). 1271 Related silylarsenides [As(H)-SiR 3 ] − of strontium, barium, magnesium, zinc and lithium were also reported.…”