Intramolecular coupling of acetylenic groups of bis(alkynyl)phosphanes and silanes mediated by benzynezirconocene: a route to new mono- and tricyclic heterocycles
Benzo-zirconacyclohexadiene-phospha or silacyclobutene fused ring systems are easily prepared via a benzynezirconocene intermediate by means of thermolysis of Cp 2 ZrPh 2 in the presence of bis(alkynyl)phosphanes or silanes. These polyunsaturated systems are the source of a variety of new mono- or tricyclic heterocycles incorporating either one or two heteroatoms.
Synthesis, microwave spectrum, quantum chemical calculations, and conformational composition of a novel primary phosphine, cyclopropylethynylphosphine, (C3H5C≡CPH2).
International audience; The microwave spectrum of cyclopropylethynylphosphine, C3H5C≡CPH2, has been investigated in the 26-120 GHz spectral region. The spectrum is dominated by very rich and complex a-type R-branch pile-ups. There must be insignificant steric interaction between the phosphino group and the cyclopropyl ring due to the long distance between these two groups. However, the phosphino group does not undergo free or nearly free internal rotation. Instead, the spectra of two distinct conformers were assigned. Both these two forms have CS symmetry. The symmetry plane bisects the cyclopropyl ring and the phosphino group in both conformers, and the lone electron pair of the phosphino …