Electron-transfer chemistry of (Me/sub 5/C/sub 5/)/sub 2/Yb: cleavage of diorganoperoxide and related chalcogenides to give (Me/sub 5/C/sub 5/)/sub 2/Yb(ER)(L) (E = O, S, Se, or Te; L = a Lewis base). Crystal structure of (Me/sub 5/C/sub 5/)/sub 2/Yb(TePh)(NH/sub 3/)
The divalent metallocenes of ytterbium (Me/sub 5/C/sub 5//sub 2/)(OEt/sub 2/) or (Me/sub 5/C/sub 5/)/sub 2/Yb(NH/sub 3/)/sub 2/ react with molecules of the type REER to give the trivalent ytterbium complexes (Me/sub 5/C/sub 5/)/sub 2/Yb(ER)(L), where L is OEt/sub 2/ or NH/sub 3/, E is S, Se, or Te, and R is a phenyl or substituted phenyl group. The ammonia complexes are easier to characterize than the diethyl ether complexes since the latter complexes lose ether in the solid state and give unsatisfactory microanalytical data whereas the ammonia complexes give satisfactory elemental analyses. In addition, the line width of the Me/sub 5/C/sub 5/ protons in the /sup 1/H NMR spectra of the diethyl ether complexes is ca. 500 Hz whereas the line width at half-height is ca. 50 Hz for the ammonia complexes, consistent with the notion that the barrier to chemical exchange is higher for the ammonia complexes. The peroxides ROOR, where R is Me/sub 3/C or Me/sub 3/Si, give the alkoxides (Me/sub 5/C/sub 5/)/sub 2/Yb(OR)(NH/sub 3/), and Et/sub 2/NC(S)SS(S)CNEt/sub 2/ gives the known (Me/sub 5/C/sub 5/)/sub 2/Yb(S/sub 2/CNEt/sub 2/). In contrast, dialkyl dithiophosphinates give (Me/sub 5/C/sub 5/)/sub 2/Yb(S/sub 2/PR/sub 2/) and R/sub 2/PPR/sub 2/, where R is Me or Et. The synthetic routes developed developed in this work are the best methods currently available for synthesis of these trivalent species. The crystal structure of (Me/sub 5/C/sub 5/)/sub 2/Yb(TePh)(NH/sub 3/) has been done. The crystals are orthorhombic, P2/sub 1/2/sub 1/2/sub 1/, with a = 11.823 (3) /angstrom/, b = 25.917 (6) /angstrom/, c = 8.539 (2) /angstrom/, and V = 2616.5 /angstrom//sup 3/. For Z = 4, the calculated density is 1.69 g cm/sup /minus/3/. The Yb-Te distance is 3.039 (1) /angstrom/, and the Yb-Te-C(Ph) angle is 113.0 (3)/degree/.
- Research Organization:
- Lawrence Berkeley Lab., CA (USA)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5975968
- Journal Information:
- Organometallics; (United States), Vol. 7:8
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKENES
CRYSTAL STRUCTURE
YTTERBIUM COMPLEXES
CHEMICAL PREPARATION
ELECTRON TRANSFER
EXPERIMENTAL DATA
HYDROGEN 1
LATTICE PARAMETERS
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
SPACE GROUPS
X-RAY DIFFRACTION
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
RARE EARTH COMPLEXES
RESONANCE
SCATTERING
SPECTRA
STABLE ISOTOPES
SYNTHESIS
400201* - Chemical & Physicochemical Properties