Ab Initio Study of the Wolff Rearrangement of C₆H₄0 Intermediate in the Gas Phase

Journal Article · Thu Sep 30 00:00:00 EDT 1999 · Russian Chemical Bulletin

DOI:https://doi.org/10.1007/BF02494806· OSTI ID:949943

Borisov, Yurii A. ^[1]; Garrett, Bruce C. ^[2]; Feller, David F. ^[2]

---

1. Russian Academy of Sciences (RAS), Moscow (Russian Federation)
2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Ab initio calculations of the geometry and reactivity of 1,2-ketocarbene C₆H₄O as an intermediate in organic reactions were performed using the second-order Møller-Plesset (MP2) perturbation theory in the 6-311G* basis set. Only the singlet state of the intermediate was considered. An oxirene-like structure (6) with a six-membered ring and a ketene-like structure (5) with a five-membered ring were localized on the potential energy surface. Attempts to locate a quinone type structure characteristic of aliphatic ketocarbenes failed. The energy of structure5 is -70 kcal mol^-1 lower than that of structure 6. Harmonic frequencies and intensities of normal vibrations in the IR spectra of6 and5 were calculated. The activation energy of the Wolff rearrangement 6→5 was estimated at 12.5 kcal mol^-1. The geometry of the transition state of this reaction resembles the quinone-like structure.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 949943
• Report Number(s): PNNL-SA--32857; KC0301020
• Journal Information: Russian Chemical Bulletin, Journal Name: Russian Chemical Bulletin Journal Issue: 9 Vol. 48; ISSN 1066-5285
• Country of Publication: United States
• Language: English

Related Subjects

1
2-ketocarbene C6H4O
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACTIVATION ENERGY
BENZOQUINONES
MOLECULAR STRUCTURE
Moller-Plesset perturbation theory
PERTURBATION THEORY
POTENTIAL ENERGY
REACTION INTERMEDIATES
Wolff rearrangement
ab initio quantum-chemical calculations
activation energy
frequencies of normal vibrations
intermediates in organic reactions
ketene-like structure
molecular and electronic structure
oxirene-like structure