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

Journal Article · Mon Jan 01 00:00:00 EST 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00115a018· OSTI ID:6880934

Stults, S D; Andersen, R A; Zalkin, A ^[1]

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1. 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), Vol. 9:1; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CERIUM COMPLEXES
CRYSTAL STRUCTURE
COORDINATION VALENCES
DATA ANALYSIS
EXPERIMENTAL DATA
MEASURING INSTRUMENTS
MEASURING METHODS
ORGANOMETALLIC COMPOUNDS
COMPLEXES
DATA
INFORMATION
NUMERICAL DATA
ORGANIC COMPOUNDS
RARE EARTH COMPLEXES
VALENCE
400200* - Inorganic
Organic
& Physical Chemistry