Chemistry of trivalent cerium and uranium metallocenes: Reactions with alcohols and thiols

Journal Article · Tue May 01 04:00:00 EDT 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00119a039· OSTI ID:6520016

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

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1. Lawrence Berkeley Lab., CA (USA)

The trivalent cerium metallocene (Me{sub 3}CC{sub 5}H{sub 4}){sub 3}Ce reacts with alcohols, HOR (R = CHMe{sub 2} or Ph), or thiols, HSR (R = CHMe{sub 2}, or Ph), to give the dimers (Me{sub 3}CC{sub 5}H{sub 4}){sub 4}Ce{sub 2} ({mu}-ER){sub 2} as shown by X-ray crystallography for the isopropoxide and isopropylthiolate derivatives. Crystals of (Me{sub 3}CC{sub 5}H{sub 4}){sub 4}Ce{sub 2}({mu}-OCHMe{sub 2}){sub 2} are monoclinic, P2{sub 1}/c with a = 11.962 (4) {angstrom}, b = 14.489 (5) {angstrom}, c = 12.384 (5) {angstrom}, {beta} = 103.31 (3){degree}, and V = 2,089 {angstrom}{sup 3}; the structure was refined by full-matrix least-squares methods to a conventional R factor for 0.028, 2,874 data, F{sup 2} > 2{sigma}(F{sup 2}). Crystals of (Me{sub 3}CC{sub 5}H{sub 4}){sub 4}Ce{sub 2}({mu}-SCHMe{sub 2}){sub 2} are also monoclinic, P2{sub 1}/n with a = 14.255 (9) {angstrom}, b = 13.585 (9) {angstrom}, c = 11.265 (7) {angstrom}, {beta} = 96.02 (5){degree}, V = 2,170 {angstrom}{sup 3}. The uranium metallocene (Me{sub 3}CC{sub 5}H{sub 4}){sub f3}U reacts with HSPh at low temperature to give isolable (Me{sub 3}CC{sub 5}H{sub 4}){sub 3}USPh and unidentified material.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6520016
• Journal Information: Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:5; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTINIDE COMPLEXES
ALCOHOLS
CERIUM COMPLEXES
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
HYDROXY COMPOUNDS
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
RARE EARTH COMPLEXES
SYNTHESIS
THIOLS
URANIUM COMPLEXES