SYNTHESIS AND REACTIVITY OF FUNCTIONALIZED RHENIUM GERMYL COMPLEXES (ETA5-C5H5)RE(NO)(PPH3)(GEPH2X) - DYNAMIC EQUILIBRIA WITH GERMYLENE COMPLEX [(ETA5-C5H5)RE(NO)(PPH3)(=GEPH2)]+X- Academic Article uri icon

abstract

  • Reaction of Li+[(5-C5H5)Re(NO)(PPh3)]- with Ph3GeCl and Ph2GeCl2 (THF, -75C) gives germyl complexes (5-C5H5)Re(NO)(PPh3)(GePh3) (84%) and (5-C5H5) Re(NO)(PPh3)(GePh2Cl) (3, 82%), respectively. Reaction of 3 and (CH3)3SiOTf gives (5-C5H5)Re(NO)(PPh3)(GePh2OTf) (4, 82%). Several properties show the triflate substituent in 4 to be extremely labile. First, reaction of 4 and pyridine to give [(5- C5H5)Re(NO)(PPh3)(GePh2NC5H5)]+TfO- (5) is complete in < 5 min at -78C; the pyridine in 5 rapidly exchanges with pyridine-d5 (CD2Cl2, -80C). Second, the 13C NMR resonances of the diastereotopic germanium phenyl substituents in 4 coalesce upon warming (G268K (CD2Cl2) = 12.60.2 kcal mol-1). The most likely mechanisms for this dynamic behaviour entail initial triflate dissociation to give the germylene complex [(5-C5H5)Re(NO)(PPh3)( GePh2)]+TfO-. 1988.

published proceedings

  • POLYHEDRON

author list (cited authors)

  • LEE, K. E., & GLADYSZ, J. A.

citation count

  • 7

complete list of authors

  • LEE, KE||GLADYSZ, JA

publication date

  • January 1988