Divalent lanthanide chemistry. Preparation and crystal structures of sodium tris(bis(trimethylsilyl)amido)europate(II) and sodium tris(bis(trimethylsilyl)amido)ytterbate(II), NaM(N(SiMe/sub 3/)/sub 2/)/sub 3/
A new synthetic method for high-yield preparations of the divalent silylamides M(N(SiMe/sub 3/)/sub 2/)/sub 2/(MeOCH/sub 2/CH/sub 2/OMe)/sub 2/, where M is Eu or Yb (Me methyl), has been developed that involves reaction of MI/sub 2/ and NaN(SiMe/sub 3/)/sub 2/ in MeOCH/sub 2/CH/sub 2/OMe. Reaction of EuI/sub 2/ and NaN(SiMe/sub 3/)/sub 2/ in Et/sub 2/O (ethyl ether) yields NaEu(N(SiMe/sub 3/)/sub 2/)/sub 3/. Reaction of YbI/sub 2/ with NaN(SiMe/sub 3/)/sub 2/ in Et/sub 2/O yields two products depending upon the crystallization conditions. If Et/sub 2/O is used, Yb(N(SiMe/sub 3/)/sub 2/)/sub 2/(OEt/sub 2/)/sub 2/ is isolated. In contrast, if toluene is used, NaYb(N(SiMe/sub 3/)/sub 2/)/sub 3/ is isolated. The structures were refined to conventional R factors of 0.031 (6757 data, F/sup 2/ > sigma(F/sup 2/)) for the Eu complex and 0.056 (2546 data, F/sup 2/ > 3 sigma(F/sup 2/)) for the Yb complex. In the europium complex there are two crystallographically distinct, but chemically equivalent, molecules. The molecular structures of the Eu and Yb complexes are similar. The lanthanide atom bonds to one of the silylamide ligands exclusively and shares the two others with the sodium atom. The Eu-N and Yb-N (unshared) distances are 2.46 (1) and 2.38 (2) A, respectively; the average Eu-N and Yb-N (shared) distances are 2.55 (2) and 2.46 (2) A, respectively; the average Na-N distance is 2.46 (1) A. Several noteworthy close contacts between the metal ions and methl carbon atoms have been noted, i.e. Na-C = 2.71 A, Eu-C = 2.97 A, and Yb-C = 2.86 A. 16 references, 4 figures, 4 tables.
- Research Organization:
- Univ. of California, Berkeley
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6455890
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 23:15; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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ALKALI METAL COMPLEXES
ALKANES
AMIDES
BOND ANGLE
COHERENT SCATTERING
COMPLEXES
CORRELATIONS
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
DENSITY
DIFFRACTION
DISTANCE
EUROPIUM COMPLEXES
EXPERIMENTAL DATA
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INTERATOMIC DISTANCES
LATTICE PARAMETERS
LEAST SQUARE FIT
LIGANDS
MATHEMATICAL MODELS
MAXIMUM-LIKELIHOOD FIT
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
NUMERICAL DATA
NUMERICAL SOLUTION
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SILICON COMPOUNDS
ORTHORHOMBIC LATTICES
PHYSICAL PROPERTIES
RARE EARTH COMPLEXES
SCATTERING
SILANES
SILICON COMPOUNDS
SODIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
X-RAY DIFFRACTION
YTTERBIUM COMPLEXES