This paper reports two series of lanthanide -carbocydic complexes of formula K[Ln(C8Hs)2] and [Ln(C8H8)Cl • 2C4H80]2. Single crystal X-ray structures of the cerium member of both series have been previously determined. Analytical and spectral data strongly suggest that the other lanthanide complexes in each series are isostructural with the cerium complexes. Chemical and spectral data show that these lanthanide cyclooctatetraenyl metallocenes are highly ionic relative to the analogous actinide complexes. This trend undoubtedly results from the inability of the lanthanide 4f orbitals to contribute to covalent bonding relative to the 5f orbitals. Similar properties are found for the corresponding complex with yttrium, a metal which is not a lanthanide rare earth. Using (17) F.
Ruthenium trichloride catalyses the homogeneous oxidation of secondary alcohols to ketones, primary amines to nitriles, and 2-aminoalkanes to imines by 0,; this is the first example of a homogeneous catalytic oxidation of an amino-group.
Details are given for the preparation of "uranocene," U(C8H8)2, from UC14 and CSH82-in THF. Uranocene reacts only slowly with water or acetic acid but decomposes with oxygen, bases, and strong acids. It does not undergo electrophilic substitutions or metallation reactions. Its chemistry is discussed in terms of a simple theory of the electronic structure that involves covalent interaction of the highest occupied e2u ligand MO's with metal fx yi and f(z= _ AO's.
Unique properties of metallocarborane sandwich anions of the type [(C2B9H11)2M(III)]- as chemical stability, specific reactivity, very strong acidity of conjugated acids along with an extreme organophility of their salts and a very limited solubility of the salts with organic cations in water are discussed. The application of metallocarboranes to analysis, characterization and isolation of organic bases, including alkaloids, amino acids, amides, etc., from very diluted water solutions is suggested and demonstrated on some examples.
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