Cationic actinide metallocene alkyls and hydrides. Metal bis(dicarbollides) as counterions

Journal Article · Fri Oct 01 04:00:00 EDT 1993 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00034a079· OSTI ID:5526106

Yang, X; King, W A; Sabat, M; Marks, T J ^[1]

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1. Northwestern Univ., Evanston, IL (United States)

Metal bis(dicarbollides) of the type M(B[sub 9]C[sub 2]H[sub 11])[sub 2][sup [minus]] (M = Co, Fe) have been incorporated into cationic organothorium complexes [Cp[prime][sub 2]ThR][sup +]X[sup [minus]] (Cp[prime] = [eta][sup 5]-(CH[sub 3])[sub 5]C[sub 5]; R = alkyl, H) as potential weakly coordinating anions. The reaction of Cp[prime][sub 2]Th(CH[sub 3])[sub 2] with [HNEt[sub 3]][sup +]Co(B[sub 9]C[sub 2]H[sub 11])[sub 2][sup [minus]] and [HNEt[sub 3]][sup +] [Fe(B[sub 9]C[sub 2]H[sub 11])[sub 2]][sup [minus]] in hydrocarbon solvents affords [Cp[prime][sub 2]ThCH[sub 3]][sup +] Co(B[sub 9]C[sub 3]H[sub 11])[sub 2][sup [minus]] and [Cp[prime][sub 2]ThCH[sub 3]][sub 2][sup 2+] [Fe(B[sub 9]C[sub 2]H[sub 11])[sub 2]][sup 2[minus]] (2), respectively. The structure of 2 reveals tight ion-pairing with three close Th-H-B bridging interactions (2.42(3), 2.50(3), 2.67-(4) A). This level of Th coordinative saturation explains the unexpected chemical inertness of 1 and 2. The reaction of Cp[prime][sub 2]Th[CH[sub 2]Si(CH[sub 3])[sub 3]][sub 2] with [HNEt[sub 3]][sup +]Co(B[sub 9]C[sub 2]H[sub 11])[sub 2][sup [minus]] affords [Cp[prime][sub 2]ThCH[sub 2]Si(CH[sub 3])[sub 3]][sup +] [Co(B[sub 9]C[sub 2]H[sub 11])[sub 2]][sup [minus]] (3), which slowly undergoes hydrogenolysis to yield [Cp[prime][sub 2]ThH][sup +] [Co(B[sub 9]C[sub 2]H[sub 11])[sub 2]][sup [minus]] (4). 18 refs., 2 figs., 3 tabs.

• DOE Contract Number: FG02-86ER13511
• OSTI ID: 5526106
• Journal Information: Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 12:10; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ACTINIDE COMPLEXES
ACTINIDES
ALKENES
CATALYSTS
CHEMICAL REACTIONS
COMPLEXES
DATA
ELEMENTS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
METALS
MOLECULAR STRUCTURE
NMR SPECTRA
NUMERICAL DATA
ORGANIC COMPOUNDS
POLYMERIZATION
SPECTRA
SYNTHESIS
THORIUM COMPLEXES