A Computational Investigation of the Stability of Cyclopropyl Carbenes

Bulletin of the Korean Chemical Society

Volumn 25, Issue 1, 2004, Pages 90-96

  Baik, Woonphil ^a   Yoon, Cheol Hun ^a   Koo, Sangho ^a   Kim, Byeong Hyo ^b  

^a Myong Ji University   (South Korea)

^b Kwangwoon University   (South Korea)

Author keywords

B3LYP; Carbene; Conformation; Stabilization energy

Indexed keywords

AZO COMPOUND; CARBENOID; CYCLOPROPANE DERIVATIVE; CYCLOPROPYLCARBENE DERIVATIVE; DICYCLOPROPYLCARBENE DERIVATIVE; DIISOPROPYLCARBENE DERIVATIVE; ISOPROPYLCARBENE DERIVATIVE; PROPANE; UNCLASSIFIED DRUG;

ARTICLE; CALCULATION; CHEMICAL BOND; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CONJUGATION; DECOMPOSITION; DENSITY FUNCTIONAL THEORY; ENERGY; EVALUATION; GEOMETRY; MOLECULAR STABILITY; STRUCTURE ANALYSIS;

EID: 1642462295     PISSN: 02532964     EISSN: None     Source Type: Journal    
DOI: 10.5012/bkcs.2004.25.1.090     Document Type: Article

References (44)

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31. The density functional theory calculations used Becke's three-parameter hybrid method (Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652) and the correlation functional of Lee (Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 785-789) within the Gaussian 94 program. The zero-point energies were corrected by a scaling factor of 0.9804 to eliminate known systematic errors in the calculated frequency.
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39. In the bisected conformation, the vacant carbenic p orbital can favorably interact with the bent cyclopropyl bonds. A bisected conformation of cyclopropylmethylene was proposed by Hoffmann with an LCAO MO calculation of the extended Hückel type. See: Hoffmann, R.; Zeiss, G. D.; Van Dine, G. W. J. Am. Chem. Soc. 1968, 90, 1485. The optimized geometry for cyclopropylmethylene at HF/3-31G level also shows a bisected conformation. See ref. 8b.
40. The experimental bond length in cyclopropane is 1.512 Å. The calculated bond angle and bond length for cyclopropane are 60.04° and 1.508 Å at the B3LYP/6-31G(d) + ZPE level. See: Bastiansen, O.; Fritsch, F. N.; Hedberg, K. Acta Crystallogr. 1964, 17, 538.
41. The ideal value for the bond angle at the carbene center in singlet methylene is only 102°. Sterically hindered substituents force a widening of this bond angle. For example, the bond angles for dimethylcarbene and di-tert-butylcarbene at the B3LYP/TZ2P level are 113.5° and 125.1°, respectively. See ref. 16.
42. The experimental Singlet-Triplet (S-T) splitting of methylene is 9.05 ± 0.06 kcal/mol, while at the B3LYP/6-31G* level the S-T for methylene is 13.56 kcal/mol, 4.09 kcal/mol more than the experimental result. Thus, the computed S-T splittings of carbenes 1-3 in Table 5 are corrected by 4.09 kcal/mol to account for the overestimation. This analysis followed the approach used by Sulzbach et al. See: Sulzbach, H. M.; Bolton, E.; Lenoir, D.; Schleyer, P. v. R.; Schaefer III, H. F. J. Am. Chem. Soc. 1996, 118, 9908.
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