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Studies concerning the chemistry of rare earth elements in organic environments Crease, Allan Edward

Abstract

The infrared and proton magnetic resonance spectra of a number of compounds containing sites of Lewis basicity change in the presence of selected cyclopentadienyllanthanides, R3Ln. These spectral changes indicate that the lanthanide derivatives can act as Lewis acids towards bases such as bridging and terminal carbonyl ligands, terminal nitrosyl ligands, appropriate transition metals and a carbon-carbon triple bond. Several solid adducts can be isolated and characterized. The preparation of the new compounds R2LnM(_5-Cp)(C0)3 [Ln = Dy, Ho, Er or Yb; M = Mo or W] is described, and evidence for the existence of isocarbonyl linkages in these complexes is presented. As a synthetic route to compounds containing apparent lanthanide-transition element bonds, the direct reaction of elemental metals with transition metal organometal1ics is studied. Finely divided lanthanide and other metals react with substrates such as Mn(C0)5Br, (3-C3H5)Fe(C0)3I, [(5-Cp)Mo(C0)3]2 and (5-Cp)Cr(C0)3HgCl in THF to yield extremely reactive, air- and moisture-sensitive solutions. Some of the chemistry of these solutions and other synthetic approaches to them are outlined. The versatility of these solutions as reactive intermediates during the preparation of organometallic compounds is described.

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