Ion chemistry and gas-phase basicity of nickelocene by ion cyclotron resonance spectroscopy

Journal Article · Sun Feb 29 23:00:00 EST 1976 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50157a034· OSTI ID:7283030

Corderman, R D; Beauchamp, J L

The gas-phase ion chemistry of bis(eta/sup 5/-cyclopentadienyl)nickel (nickelocene) is studied using the techniques of ion cyclotron resonance spectroscopy. Total rate constants for the reactions of the primary fragment ions at 70 eV are determined using trapped-ion methods. The long-lived nickelocene anion, Ni(C/sub 5/H/sub 5/)/sub 2//sup -/, is formed directly by electron attachment and is unreactive with a variety of simple molecules. Nickelocene is observed to be an exceptionally strong base in the gas phase. Equilibrium proton-transfer reactions are observed in mixtures of nickelocene with (CH/sub 3/)/sub 3/N and (C/sub 2/H/sub 5/)/sub 2/NH, from which the gas-phase basicity or proton affinity (PA) is determined to be 218.9 +- 1.0 kcal/mol relative to PA(NH/sub 3/) = 201 +- 1 kcal/mol. Attempts to determine the site of protonation were inconclusive. The ion chemistry and base strength of nickelocene and ferrocene are compared. (auth)

• Research Organization: California Inst. of Tech., Pasadena
• OSTI ID: 7283030
• Journal Information: Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 15:3; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ANIONS
BASES
CHARGED PARTICLES
COMPLEXES
DIENES
FLUIDS
GASES
HYDROCARBONS
ION CYCLOTRON RESONANCE SPECTROSCOPY
ION SPECTROSCOPY
IONS
NICKEL COMPLEXES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
POLYENES
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES