Structural studies on cyclopentadienyl compounds of trivalent cerium: Tetrameric (MeC sub 5 H sub 4 ) sub 3 Ce and monomeric (Me sub 3 SiC sub 5 H sub 4 ) sub 3 Ce and ((Me sub 3 Si) sub 2 C sub 5 H sub 3 ) sub 3 Ce and their coordination chemistry
- Univ. of California, Berkeley (USA)
The coordinated tetrahydrofuran in (MeC{sub 5}H{sub 4}){sub 3}Ce(THF) can be removed by Me{sub 3}Al in a Lewis acid-base reaction or by the toluene-reflux method to give base-free (MeC{sub 5}H{sub 4}){sub 3}Ce which is a monomer in the gas phase though a tetramer in the solid state: monoclinic, P2{sub 1}/a, with a = 12.497 (5) {angstrom}, b = 26.002 (8) {angstrom}, c = 9.664 (3) {angstrom}, {beta} = 97.33 (3){degree}; R = 0.041 for 2,117 data, F{sup 2} > 2{sigma}(F{sup 2}). The structure is made up of a cyclic tetramer in which two MeC{sub 5}H{sub 4} rings are {eta}{sup 5}-bonded to each cerium atoms and one MeC{sub 5}H{sub 4} ring is bridging two cerium atoms such that the MeC{sub 5}H{sub 4} ring is {eta}{sup 5}-bonded to one cerium and {eta}-{sup 1}-bonded to the other. With larger cyclopentadienyl groups, the binary metallocenes ({eta}{sup 5}-Me{sub 3}SiC{sub 5}H{sub 4}){sub 3}Ce, ({eta}{sup 5}-Me{sub 3}CC{sub 5}H{sub 4}){sub 3}Ce, and ({eta}{sup 5}-(Me{sub 3}Si){sub 2}C{sub 5}H{sub 3}){sub 3}Ce are monomeric in the gas phase and the solid state. The structure of the latter is based upon a trigonal-planar geometry the crystals are monoclinic, I2/c, with a = 22.752 (5) {angstrom}, b = 11.386 (3) {angstrom}, c = 17.431 (4) {angstrom}, {beta} = 105.70 (3){degree}, R = 0.046 for 2,519 data, and F{sup 2} > 3{sigma}(F{sup 2}).
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 6880934
- Journal Information:
- Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:1; ISSN ORGND; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400200* -- Inorganic
Organic
& Physical Chemistry
CERIUM COMPLEXES
COMPLEXES
COORDINATION VALENCES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RARE EARTH COMPLEXES
VALENCE