Cationic Actinide Metallocene Alkyls and Hydrides. Metal Bis(dicarbollides) as Counterions

Xinmin Yang, Wayne A. King, Michal Sabat, Tobin Jay Marks*

*Corresponding author for this work

Research output: Contribution to journalComment/debate

43 Scopus citations

Abstract

Metal bis(dicarbollides) of the type M(B9-C2H11)2- (M = Co, Fe) have been incorporated into cationic organothorium complexes [Cp′2ThR]+X (Cp′ = η5-(CH3)5C5; R = alkyl, H) as potential weakly coordinating anions. The reaction of Cp′2Th(CH3)2 with [HNEt3]+-[Co(B9C2H11)2] and [HNEt3]+[Fe(B9C2H11)2] in hydrocarbon solvents affords [Cp•2ThCH3]+[Co(B9C2H11)2] (1) and [Cp′2ThCH3]22+[Fe(B9C2H11)2]2− (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) Å). This level of Th coordinative saturation explains the unexpected chemical inertness of 1 and 2. The reaction of Cp′2Th[CH2Si(CH3)3]2 with [HNEt3]+− [Co(B9C2H11)2] affords [Cp′2ThCH2Si(CH3)3]+− [Co(B9C2H11)2] (3), which slowly undergoes hydrogenolysis to yield [Cp′2ThH]+ [Co(B9C2H11)2] (4).

Original languageEnglish (US)
Pages (from-to)4254-4258
Number of pages5
JournalOrganometallics
Volume12
Issue number10
DOIs
StatePublished - Jan 1 1993

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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