Ion chemistry and gas-phase basicity of nickelocene by ion cyclotron resonance spectroscopy
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. 39 references, 2 figures, 3 tables.
- OSTI ID:
- 6536058
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 15:3; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKANES
AMINES
ANIONS
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COLLISIONS
COMPLEXES
CYCLOALKANES
DATA
ELECTRONS
ELEMENTARY PARTICLES
ENERGY RANGE
EV RANGE
EV RANGE 10-100
EXPERIMENTAL DATA
FERMIONS
FLUIDS
GASES
HIGH VACUUM
HYDROCARBONS
INFORMATION
ION COLLISIONS
ION CYCLOTRON RESONANCE SPECTROSCOPY
ION SPECTROSCOPY
ION-MOLECULE COLLISIONS
IONS
KINETICS
LEPTONS
MASS SPECTRA
MOLECULE COLLISIONS
NICKEL COMPLEXES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PRESSURE DEPENDENCE
REACTION KINETICS
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
TRAPPING
YIELDS