Fluoro complexes of permethyltantalocene, Cp{sup *}{sub 2}TaF{sub 3}(Cp{sup *} = C{sub 5}Me{sub 5}) and [Cp{sup *}{sub 2}TaF{sub 2}][BF{sub 4}]: Facile formation of a tetrafluoroborate complex via corrosion of borosilicate glass

Journal Article · Mon Dec 21 04:00:00 EST 1998 · Organometallics

DOI:https://doi.org/10.1021/om980549v· OSTI ID:315988

Shin, J H; Parkin, G ^[1]

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1. Columbia Univ., New York, NY (United States). Dept. of Chemistry

The trihydride complex Cp{sup *}{sub 2}TaH{sub 3} (Cp{sup *} = C{sub 5}Me{sub 5}) is a convenient precursor to a series of halide derivatives, which include unusual examples of organometallic fluoride complexes. Most interestingly, reaction of Cp{sup *}{sub 2}TaH{sub 3} with (C{sub 5}H{sub 5}N)(HF){sub x} affords the trifluoride complex Cp{sup *}{sub 2}TaF{sub 3} when carried out in a plastic vessel, but the tetrafluoroborate complex [Cp{sup *}{sub 2}TaF{sub 2}][BF{sub 4}] when performed in a borosilicate glass vessel. In contrast, reaction of Cp{sup *}{sub 2}TaH{sub 3} with [Et{sub 3}N(HF){sub 3}] results in cleavage of one of the pentamethylcyclopentadienyl ligands to yield the half-sandwich complex [Et{sub 3}NH][Cp{sup *}TaF{sub 5}]. Cp{sup *}{sub 2}TaF{sub 3} and [Cp{sup *}{sub 2}TaF{sub 2}][BF{sub 4}] may be readily interconverted. Thus, treatment of Cp{sup *}{sub 2}TaF{sub 3} with either Et{sub 2}O{center_dot}BF{sub 3} or LiBF{sub 4} yields [Cp{sup *}{sub 2}TaF{sub 2}][BF{sub 4}], while reaction of the latter complex with excess NaF regenerates Cp{sup *}{sub 2}TaF{sub 3}. Furthermore, Cp{sup *}{sub 2}TaF{sub 3} is converted to the cyano fluoride complex Cp{sup *}{sub 2}Ta(CN){sub 2}F upon reaction with excess Me{sub 3}SiCN. Sequential replacement of the hydride ligands of Cp{sup *}{sub 2}TaH{sub 3} is observed in the reaction with MeI to give Cp{sub 2}TaH{sub 2}I and Cp{sup *}{sub 2}TaHI{sub 2}; likewise, the reactions of Cp{sup *}{sub 2}TaH{sub 3} with either HCl, CHCl{sub 3}, or CCl{sub 4} give Cp{sup *}{sub 2}TaH{sub 2}Cl and Cp{sup *}{sub 2}TaHCl{sub 2}. The molecular structures of [Cp{sup *}{sub 2}TaF{sub 2}][BF{sub 4}], [Et{sub 3}NH][Cp{sup *}TaF{sub 5}], and Cp{sup *}{sub 2}TaHCl{sub 2} have been determined by X-ray diffraction.

• Sponsoring Organization: USDOE, Washington, DC (United States)
• DOE Contract Number: FG02-93ER14339
• OSTI ID: 315988
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 26 Vol. 17; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
BOROSILICATE GLASS
EXPERIMENTAL DATA
FLUOROBORATES
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
SYNTHESIS
TANTALUM COMPLEXES
X-RAY DIFFRACTION