Summary
Many organic C-nitroso compounds R-NO form stable dimers with a covalent NN bond. To gain insight into the dimerization reaction 2 R-NO ↓ (R-NO)2 a theoretical study of the dimerization to atrans-form was performed using HNO as a model compound. Complete geometry optimizations were carried out at the HF, MP2 and QCISD levels using a 6–31G* basis. In the stationary points energies were calculated at the MP4(SDTQ) and QCISD(T) levels. For the equilibrium structure of the monomer and dimers stable RHF solutions were found, whereas for the TS UHF and UMPn calculations were applied. Extensive spin contamination was found in the UHF wavefunction, and projections up tos+4 were invoked. Relative energies were corrected for differences in ZPE. Calculations were made (a) for the least-motion path (C 2h symmetry) and (b) for a path with complete relaxation of all internal coordinates. Along the latter path a TS having virtuallyC i symmetry was found. Along path (a) an activation energy of around 150 kcal/mol was predicted, in conformity with a symmetry forbidden reaction. On the relaxed path (b) the barrier to dimerization was estimated to be 10.7 kcal/mol at the MP4(SDTQ)//MP2 level, and 10.9 kcal/mol at the QCISD(T)//QCISD level. Unscaled ZPE corrections, calculated at the SCF level, changed these values to 12.7 and 12.9 kcal/mol, respectively. The reaction energy for the dimerization process is predicted to be − 17.2 kcal/mol at the MP4(SDTQ)//MP2 level corrected for ZPE. Calculations at the G1 level gave a corresponding value of − 16.4 kcal/mol. The equilibrium constant for the association to thetrans dimer is estimated to beK p =259 atm, indicating that the dimer should be an observable species in the gas phase.
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References
Baly C, Desch N (1908) J Chem Soc 93:1747
Piloty O (1898) Ber Dt Chem Ges 31:456,1878; (1901) ibid 34:1863; (1902) ibid 35:3090,3101
Darwin C, Hodgkin DC (1950) Nature 166:827
Fenimore CP (1950) J Am Chem Soc 72:3226
Lüttke W (1954) J Physique et la Radium 15:633
Lüttke W (1955) Angew Chem 67:235; (1956) ibid 68:417; (1957) ibid 69:99
Lüttke W (1956) Habilitationsschrift Univ Freiburg i. Br.
Lüttke W (1957) Z f Elektrochemie 61:302,976
Kübler R, Lüttke W, Weckherlin S (1960) Z f Elektrochemie 64:657
Hammick DL (1931) J Chem Soc 3105
Chilton HTJ, Gowenlock BG, Trotman J (1955) Chem and Ind 538
Gowenlock BG, Trotman J (1955) J Chem Soc 4190; (1956) ibid 1670
van Meersche M, Germain G (1959) Bull Soc Chim Belges 68:24411
Germain G, Piret P, van Meersche M (1963) Acta Cryst 16:109
Leroy G, van Meersche, M, Germain G (1963) J Chim. Physique 1282; Leroy G, Martin P, Peeters D (1974) ibid 319
Orgel LE (1953) J Chem Soc 1276
Wu AA, Peyerimhoff SD, Buenker RJ (1975) Chem Phys Lett 35:316
Herzberg G (1966) Molecular spectra and molecular structure III: Electronic spectra and electronic structure of polyatomic molecules. Van Nostrand Reinhold, p 289, 496, 598
Gowenlock BG, Lüttke W (1958) Quart Rev Chem Soc 12:321
von Keussler V, Lüttke W (1959) Z f Elektrochemie 63:614
Tarte P (1954) Bull Soc Chim Belges 63:525
Mc Ewen KL (1961) J Chem Phys 34:547
Ha TK, Wild UP (1974) Chem Phys 4:300
Bhujle V, Wild UP, Baumann H, Wagnière G (1976) Tetrahedron 9:653
Boyer JH (1969) in: Feuer H (ed) The chemistry of the nitro and nitroso groups. Interscience, NY, Part 1, Chap 5, p 264
DMS UV atlas of organic compounds. Verlag Chemie, Weinheim, 1971, Spectrum no. C4/1
Hoffmann R, Gleiter R, Mallory FB (1970) J Am Chem Soc 92:1461
Minato T, Yamabe S, Oda H (1982) Can J Chem 60:2740
Yamabe S, Minato T, Osamura Y (1980) Int J Quant Chem 18:243
Heiberg AB (1977) Chem Phys 26:309; ibid 43:415
Christie MI, Frost JS, Voisey MA (1965) Trans Faraday Soc 61:674
Hughes MN (1968) Quart Rev Chem Soc 22:1
Kohout FC, Lampe FW (1967) J Chem Phys 46:4075
(a) He Y, Sanders WA, Lin MC (1988) J Phys Chem 92:5474;
(b) Choudhury TK, He Y, Sanders WA, Lin MC (1990) ibid 94:2394
Tsang W, Herron JT (1991) J Phys Ref Data 20:646
Coe CS, Doumani TF (1948) J Am Chem Soc 70:1516
Tarte P (1953) Bull Soc Roy Liège 22:26
Hehre WJ, Ditchfield R, Pople JA (1972) J Chem Phys 56:2257
Hariharan PC, Pople JA (1975) Theor Chim Acta 28:213
Pople JA, Head-Gordon M, Raghavachari K (1987) J Chem Phys 87:5968
Pople JA, Head-Gordon M, Fox DJ (1989) J Chem Phys 90:5622
GAUSSIAN 90 Frisch MJ, Head-Gordon M, Trucks GW, Foresman JB, Schlegel HB, Raghavachari K, Robb MA, Binkley JS, Gonzales C, Defrees DJ, Fox DJ, Whiteside RA, Seeger R, Melius CF, Baker J, Martin RL, Kahn LR, Stewart JJP, Topiol S, Pople JA (1991) Carnegie-Mellon Quantum Chemistry Publ Unit, Pittsburgh PA
Callear AB, Wood PM (1971) Trans Faraday Soc 67:3399
Krauss M (1969) J Res Natl Bur Std US 73A:191
Salotto AW, Burnelle L (1969) Chem Phys Lett 3:80
Williams GR (1975) Chem Phys Lett 30:495
Wu AA (1977) Chem Phys 21:173
Bruna PJ, Marian CM (1979) Chem Phys Lett 67:109
Heiberg A, Almløf J (1982) J Chem Phys Lett 85:542
Walch SP, Rohlfing CM (1989) J Chem Phys 91:2939
Dalby FW (1958) Can J Phys 36:1366
Petersen JC (1985) J Mol Spectrosc 110:277
Gill PMW, Radom L (1986) Chem Phys Lett 132:16
Sosa C, Schlegel HB (1986) Int J Quant Chem 29:1001
Schlegel HB (1986) J Chem Phys 84:4530
Knowles PJ, Handy NC (1988) J Chem Phys 88:6691
Yamaguchi K, Takahara Y, Fueno T, Houk KN (1988) Theor Chim Acta 73:337
Stark JG, Wallace HG (1988) Chem data book. John Murray, London
Batt L, Milne RT (1973) Int J Chem Kinet 5:1067
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Lüttke, W., Skancke, P.N. & Traetteberg, M. On the dimerization process of nitroso compounds. Theoret. Chim. Acta 87, 321–333 (1994). https://doi.org/10.1007/BF01113388
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DOI: https://doi.org/10.1007/BF01113388