Metal Alkylidene Chemistry of RCP

We have been studying the organometallic chemistry of sterically hindered phosphaacetylenes with metal alkylidene catalysts. Phosphaacetylenes are isoelectronic with acetylenes and would potentially afford p-conjugated polymers with characteristics of semiconductors or conductors. The phosphaacetylenes react with early transition metal alkylidenes, but under rearrangements to form novel organometallic complexes. For example, t-butylphosphaacetylene reacts with molybdenum alkylidenes to a new molybdenum alkylidyne through the cleavage of the CP triple bond. Warming the complex leads to the re-generation of a metallocyclobutane, but with one of the alkoxide ligands shifted from molybdenum to phosphorus.

Jamison, Gregory M.; Saunders, Randall S.; Wheeler, David R.; McClain, Mark D.; Loy, Douglas A.; Ziller, Joseph W. Cycloaddition of Phosphaalkynes to High-Oxidation-State Metal Alkylidenes: Synthesis and Characterization of a Unique Phosphametallacyclobutene via an Alkoxide Ligand Shift. Organometallics (1996), 15(1), 16-18.

Jamison, Gregory M.; Saunders, Randall S.; Wheeler, David R.; Alam, Todd M.; McClain, Mark D.; Loy, Douglas A.; Ziller, Joseph W. Isolation and Characterization of the Molybdenum Alkylidyne Complex [(F3C)Me2CO]2Mo(C-t-Bu)[N(Ar)P:C(H)(CMe2Ph)] and Its Conversion to a Phosphamolybdacyclobutene. Organometallics (1996), 15(15), 3244-3246.

Contact: Doug Loy