C/sub 3/H/sub 5//sup -/ isomers. Experimental and theoretical studies of tautomeric propenyl ions and the cyclopropyl anion in the gas phase

Journal Article · Wed May 28 00:00:00 EDT 1986 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00271a012· OSTI ID:5583376

Froelicher, S W; Freiser, B S; Squires, R R

Isomeric allyl (CH/sub 2/CHCH/sub 2//sup -/), 2-propenyl (CH/sub 3/C/sup -/ = CH/sub 2/), 1-propenyl (CH/sub 3/CH = CH/sup -/), and cyclopropyl ((CH/sub 2/)/sub 2/CH/sup -/) anions, as well as the parent unsubstituted vinyl anion (C/sub 2/H/sub 3//sup -/) have been generated in the gas phase by collision-induced dissociation of the corresponding carboxylate anions by using a Fourier transform mass spectrometer (FTMS). Ion-molecule reactions of each C/sub 3/H/sub 5//sup -/ ion with selected neutral reagents are described, and distinct, non-interconverting isomeric ion structures are indicated by the results. Each of the vinylic anions and the cyclopropyl anion proton abstracts from ammonia and D/sub 2/O while the more stable allylic isomer, CH/sub 2/CHCH/sub 2//sup -/, is unreactive with the former and undergoes four hydrogen-deuterium exchanges with the latter. Sulfur abstraction from CS/sub 2/ is observed with each of the vinyl anions and the cyclopropyl anion, while the allylic ion reacts by addition followed by loss of H/sub 2/S. Four unique sets of products are produced by each of the C/sub 3/H/sub 5//sup -/ isomers in the presence of N/sub 2/O which are consistent with the expected structures. Ab initio SCF-MO calculations for each C/sub 3/H/sub 5//sup -/ ion are also described which provide additional insight into their structures and relative energies.

• Research Organization: Purdue Univ., West Lafayette, IN
• DOE Contract Number: AC02-80ER10689
• OSTI ID: 5583376
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 108:11, Issue 11
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALLYL RADICALS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
MOLECULAR STRUCTURE
AMMONIA
ANIONS
DEUTERIUM
ISOTOPE EFFECTS
HEAVY WATER
HYDROGEN
PROPYL RADICALS
SULFUR
VINYL RADICALS
CARBANIONS
EXPERIMENTAL DATA
GASES
ISOMERS
MASS SPECTRA
MASS SPECTROSCOPY
MOLECULAR ORBITAL METHOD
SELF-CONSISTENT FIELD
ALKYL RADICALS
CHARGED PARTICLES
DATA
ELEMENTS
FLUIDS
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
IONS
ISOTOPES
LIGHT NUCLEI
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
OXYGEN COMPOUNDS
RADICALS
SPECTRA
SPECTROSCOPY
STABLE ISOTOPES
SYNTHESIS
WATER
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400302 - Organic Chemistry- Isotope Effects- (-1987)