Organometallic molecule-inorganic surface coordination and catalytic chemistry. In situ CPMAS NMR delineation of organoactinide adsorbate structure, dynamics, and reactivity

Journal Article · Wed Aug 15 04:00:00 EDT 1990 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00173a009· OSTI ID:6518143

Finch, W C; Gillespie, R D; Hedden, D; Marks, T J ^[1]

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1. Northwestern Univ., Evanston, IL (USA)

A 75.4-MHz {sup 13}C CPMAS NMR spectroscopic study of the surface structures and reaction chemistry of a series of organoactinides adsorbed on various inorganic supports is reported. On Lewis acid surfaces such as dehydroxylated Al{sub 2}O{sub 3}, MgCl{sub 2}, and SiO{sub 2}-Al{sub 2}O{sub 3}, it is found that organothorium complexes of the type Cp{prime}{sub 2} ThR{sub 2} (Cp{prime} = {eta}{sup 5}-(CH{sub 3}){sub 5}C{sub 5}; R = {sup 13}CH{sub 3}, {sup 13}CH{sub 2}{sup 13}CH{sub 3}), Cp{prime}ThR{sub 3} (R = {sup 13}CH{sub 2}C{sub 6}H{sub 5}), and Cp{sub 3}ThR (Cp = {eta}{sup 5}-C{sub 5}H{sub 5}; R = {sup 13}CH{sub 3}), undergo heterolytic Th-C scission to transfer an alkyl anion to the surface forming Cp{prime}{sub 2} ThR, Cp{prime}ThR{sub 3{minus}n}, or Cp{sub 3}Th adsorbate species with cation-like character. Probe studies with paramagnetic Cp{prime}{sub 2}U({sup 13}CH{sub 3}){sub 2} indicate that the majority of the transferred methyl groups of Cp{prime}{sub 2}U({sup 13}CH{sub 3}){sub 2}/DA and Cp{prime}{sub 2}U({sup 13}CH{sub 3}){sub 2}/MgCl{sub 2} are located {approx gt}5 {angstrom} from the U(IV) ion.

• DOE Contract Number: FG02-86ER13511
• OSTI ID: 6518143
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:17; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTINIDES
CATALYSIS
DATA
DATA ANALYSIS
DYNAMICS
ELEMENTS
EXPERIMENTAL DATA
INFORMATION
MEASURING INSTRUMENTS
MEASURING METHODS
MECHANICS
METALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REACTIVITY
STRUCTURAL CHEMICAL ANALYSIS
THORIUM