84254-01-3Relevant articles and documents
Synthesis, reactivity and kinetic studies of bis(η5-cyclopentadienyl)titanium methylidene phosphine complexes
Meinhart, James D.,Anslyn, Eric V.,Grubbs, Robert H.
, p. 583 - 589 (2008/10/08)
Syntheses of several bis(η5-cyclopentadienyl)titanium methylidene phosphine complexes are reported. The titanocene methylidene phosphine complexes are generated from thermolysis of titanocene metallacyclobutanes in the presence of excess phosphine. Spectral data and reactivity are consistent with a methylidene phosphine complex rather than an ylide complex. The titanocene methylidene phosphine complexes react with olefins to form metallacyclobutanes, alkynes to form metallacyclobutenes, and CO to form a ketene complex. The phosphine ligand is labile, and an equilibrium mixture is rapidly established if a second phosphine is added. The kinetics of this equilibration and the kinetics of the reaction of titanocene methylidene phosphine complexes with alkynes and olefins are reported. The reactions proceed by rate-determining loss of phosphine followed by rapid trapping of titanocene methylidene.