Gas phase reactions of the met-cars Ti[sub 8]C[sub 12][sup +], Nb[sub 8]C[sub 12][sup +], and Ti[sub 7]NbC[sub 12][sup +] with acetone and methyl iodide

Journal Article · Thu Dec 15 00:00:00 EST 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100101a042· OSTI ID:6878913

Deng, H T; Guo, B C; Kerns, K P; Castleman, Jr, A W ^[1]

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1. Pennsylvania State Univ., University Park, PA (United States)

Gas phase reactions of the metallocarbohedrenes Ti[sub 8]C[sub 12][sup +], Nb[sub 8]C[sub 12][sup +], and Ti[sub 7]NbC[sub 12][sup +] with two different types of molecules, namely, acetone and methyl iodide, are investigated at near thermal energy by employing a laser-induced plasma source coupled with a triple quadrupole mass spectrometer. Two general types of reactions are observed: molecular associations and atom abstraction reactions. In agreement with earlier studies on the interaction of Ti[sub 8]C[sub 12][sup +]/with polar molecules, association reactions are found to dominate in the case of acetone. But, the incorporation of even one Nb greatly affects the reactivity. For example, the extraction of one and two oxygen atoms from acetone is also observed for Nb[sub 8]C[sub 12][sup +] and Ti[sub 7]NbC[sub 12][sup +]; these products are found to sequentially associate with acetone to form Nb[sub 8]C[sub 12][sup +](O)[sub 1[minus]2](acetone)[sub n] and Ti[sub 7]NbC[sub 12][sup +](O)[sub 1[minus]2](acetone)[sub n]. The reaction involves breaking C=O bonds and forming M-O bonds, evidently due to the presence of the dipole-induced charge center of Nb[sub 8]C[sub 12][sup +] and Ti[sub 7]NbC[sub 12][sup +]. Possible reaction mechanisms are proposed which take into account the electronic structures of Nb[sub 8]C[sub 12][sup +], Ti[sub 7]NbC[sub 12][sup +], and Ti[sub 8]C[sub 12][sup +]. 36 refs., 6 figs.

• OSTI ID: 6878913
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 98:50; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETONE
CHEMICAL REACTIONS
METHYL IODIDE
NIOBIUM CARBIDES
TITANIUM CARBIDES
CARBIDES
CATIONS
CHEMICAL BONDS
LASERS
MASS SPECTROSCOPY
ORGANOMETALLIC COMPOUNDS
PLASMA
VAPORS
CARBON COMPOUNDS
CHARGED PARTICLES
FLUIDS
GASES
HALOGENATED ALIPHATIC HYDROCARBONS
IODINATED ALIPHATIC HYDROCARBONS
IONS
KETONES
NIOBIUM COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
REFRACTORY METAL COMPOUNDS
SPECTROSCOPY
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400800 - Combustion
Pyrolysis
& High-Temperature Chemistry