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A Computational Study of Novel Nitratoxycarbon, Nitritocarbonyl, and Nitrate Compounds and Their Potential As High Energy Materials ⇑ Robert W

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A Computational Study of Novel Nitratoxycarbon, Nitritocarbonyl, and Nitrate Compounds and Their Potential As High Energy Materials ⇑ Robert W Computational and Theoretical Chemistry 979 (2012) 33–37 Contents lists available at SciVerse ScienceDirect Computational and Theoretical Chemistry journal homepage: www.elsevier.com/locate/comptc A computational study of novel nitratoxycarbon, nitritocarbonyl, and nitrate compounds and their potential as high energy materials ⇑ Robert W. Zoellner a, , Clara L. Lazen b, Kenneth M. Boehr b a Department of Chemistry, Humboldt State University, One Harpst Street, Arcata, CA 95521-8299, USA b Border Star Montessori School, 6321 Wornall Road, Kansas City, MO 64113-1792, USA article info abstract Article history: The Hartree–Fock RHF/6-31GÃ and density functional B3LYP/6-31G(d) methods were used to determine Received 1 June 2011 the structures and properties of the isomers of the first three members of the series Cn(CO3N)2n+2 Received in revised form 22 September 2011 (n = 0,1,2). The first member of the series, C0(CO3N)2, has six possible isomers, di(nitrato-O-)acetylene, Accepted 12 October 2011 cis- and trans-di(nitrato-O,O-)ethylene, the novel di(nitrato-O,O,O-)ethane or bis(nitratoxycarbon), Available online 22 October 2011 di(nitroso)oxalate and the mixed isomer nitroso(nitrato-O,O,O-)acetate. The most stable of these isomers, both at the Hartree–Fock or density functional levels of theory, is di(nitroso)oxalate, followed by Keywords: nitroso(nitrato-O,O,O-)acetate, and bis(nitratoxycarbon). The electronic energy of the mixed isomer clo- Nitratoxycarbon sely approximates the mean of the energies of di(nitroso)oxalate and bis(nitratoxycarbon). Neither the Nitritocarbonyl High-energy materials cis- nor the trans-di(nitrato-O,O-)ethylene could be optimized to a stable minimum on the Hartree–Fock Hartree–Fock or density functional potential energy surfaces, and the di(nitrato-O-)acetylene isomer was a stable min- Density functional imum with the Hartree–Fock method but not at the density functional level of theory. Of the two higher members of the series investigated, Cn(CO3N)2n+2 (n = 1,2), each has two isomers: the nitritocarbonyl- substituted systems — analogous to di(nitroso)oxalate — and the nitratoxycarbon-substituted systems (neglecting mixed isomers containing both nitritocarbonyl and nitratoxycarbon moieties). In these com- pounds, while the nitritocarbonyl derivatives were found to be significantly more stable thermodynam- ically than the nitratoxycarbon derivatives, both systems were stable minima on both potential energy surfaces and may be of interest as high-energy materials. Ó 2011 Elsevier B.V. All rights reserved. 1. Introduction investigated in an organic system. (The novel nitrato-O,O,O-moiety is referred to herein as a nitratoxycarbon substituent for the sake of High-energy materials — substances whose characteristics in- nomenclature simplicity and to emphasize that all three of the clude strained rings and/or cages, high nitrogen contents, and high oxygen atoms in the group are bound to the carbon center.) densities [1] — often contain nitrogen oxide moieties, such as the Simple organic molecules (essentially alkane, alkene, or alkyne nitrocarbons which contain the N-bound nitro group (–NO2). derivatives) with nitrate groups bound to a carbon atom may be Examples of these molecules include the nitrocubanes [2] and envisioned and, if fully substituted, will have the general formula hexanitrobenzene [3]. Other nitrogen oxide substituents on Cn(CO3N)2n+2, where n = 0,1,2,3, and so forth. When n = 0, the iso- organic molecules include the N-bound nitroso group (–NO) in meric molecules (1, cis-2, trans-2, 3, 4, and 5) depicted in Fig. 2 nitrosocubanes [4] and the mono-O-bound nitroxy group (– arise. Of these six molecules, none have been reported experimen- ONO2) in nitroxycubanes [1] and pentaerythritol tetranitrate tally, and calculated results have been reported in the literature (PETN) [5]. (In the latter case, the nitroxy group is formed through only for the di(nitroso)oxalate, 4 [6]. the nitration — addition of an NO2 moiety — to the alcohol rather On the other hand, when n = 1 or higher, because of the inability than the direct incorporation of a nitroxy group.) The nitroxy moi- of the molecules to form carbon–carbon double or triple bonds or ety is more exactly described as an O-bound nitrate group and, as maintain bonding to the ‘‘NO3’’ substituent without the addition of such, leads to the question of whether a nitrate group can bond to a hydrogen atoms or other substituents, only two alkane-derivative carbon center with more than one of the nitrate oxygen atoms, isomers are expected to be observed: the nitritocarbonyl analogs such as is illustrated in Fig. 1. Apparently, the nitrato-O,O- and of di(nitroso)oxalate and the nitratoxycarbon systems (ignoring the nitrato-O,O,O-bonding modes have not yet been observed or ‘‘mixed’’ isomers containing both the nitritocarbonyl and the nitratoxycarbon substituents for the sake of simplicity and compu- tational time and resources). These isomers are illustrated in Fig. 3 ⇑ Corresponding author. Tel.: +1 707 826 3244; fax: +1 707 826 3279. E-mail address: [email protected] (R.W. Zoellner). for n =1(6 and 7) and in Fig. 4 for n =2(8 and 9). If mixed isomer 2210-271X/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.comptc.2011.10.011 34 R.W. Zoellner et al. / Computational and Theoretical Chemistry 979 (2012) 33–37 Ã O O RHF/6-31G or on the B3LYP/6-31G(d) potential energy surfaces: O At the Hartree–Fock level of theory, the three calculated imaginary O N C N O C N O frequencies exhibited by each isomer represented vibrational modes which could be associated with ring-opening followed by C O O O a twisting motion, resulting in the transformation of either of the 2 isomers to 1 (but not to 4), while at the density functional level (a) (b) (c) of theory, the systems optimized to two NO moieties and an O2CCO2 structure. All attempts to locate a stable minimum for Fig. 1. Potential bonding modes for a nitrate group to a carbon center: (a) nitrato-O-, either of the 2 isomers failed at both levels of theory. (b) nitrato-O,O-, and (c) nitrato-O,O,O-. The latter mode is referred to as a At the Hartree–Fock level of theory, the most stable of these iso- nitratoxycarbon moiety for the sake of simplicity, and might also engage in mers is di(nitroso)oxalate (4), 664.4 kJ/mol more stable than di(nit- additional bonding modes through the formal lone pair of electrons on the nitrogen atom. rato-O-)acetylene (1), which itself is 365.0 kJ/mol more stable than bis(nitratoxycarbon) or di(nitrato-O-O-O-)ethane (3). Unsurpris- ingly, the electronic energy of the mixed isomer, 5, is almost ex- systems were to be considered as well, there are three additional actly intermediate between the energies of 3 and 4, and 5 is also mixed isomers for the n = 1 system and eight additional mixed iso- calculated to be thermodynamically more stable than 1 by mers for the n = 2 system. 159.6 kJ/mol. At the density functional level of theory, similar The novelty of these systems with regard to the bonding modes observations can be made, save for the result that 1 is not a stable of a nitrate group to a carbon atom and the question regarding the minimum on the potential energy surface, but rather optimizes to possible existence of these novel molecules — the highly symmet- two ONO groups and an OCCO moiety. The order of electronic ener- rical methane derivative system 7, originally constructed with sim- gies at the density functional level is the same as with the Hartree– ple ball-and-stick physical models, was the impetus for the interest Fock calculations: 4 is the most stable, 3 is least stable, and 5 is in these systems — led to the present computational investigation nearly exactly intermediate between these two molecules. How- of these molecules. Herein are reported the results for the Hartree– ever, the energy differences are larger; 4 is more stable than 5 by Fock and density functional computational investigation of the 446.1 kJ/mol and more stable than 3 by 909.0 kJ/mol. Such huge molecules with the general formula Cn(CO3N)2n+2 (n =0,1,2)at energy differences may indicate that significant difficulties will the RHF/6-31GÃ and B3LYP/6-31G(d) levels of theory. need to be overcome in order to synthesize 3 or 5, and that 4 may always be the preferred product in any synthesis. The di(nit- 2. Computational details rato-O-)acetylene species may not be accessible under any circum- stances given that 1 is not a stable minimum on the density All Hartree–Fock calculations were carried out using the PC functional energy surface despite being a minimum on the Har- Spartan Pro computational package [7] at the RHF/6-31GÃ level of tree–Fock energy surface. theory without the imposition of any symmetry constraints. Simi- Structurally, the computationally stable molecules do not ap- larly, all density functional calculations were carried out using the pear to deviate greatly from what might be considered normal Gaussian 03W computational package [8] at the B3LYP/6-31G(d) le- with respect to their overall conformations and bond distances; vel of theory without the imposition of any symmetry constraints. the calculated structures for these molecules are illustrated in Vibrational frequencies were calculated for each molecule with Fig. 5.In1, the planar mono-oxygen-bound nitrate groups are ro- each method to assure that a stable minimum on the potential en- tated with respect to each other about the very nearly linear ergy surface had been located.
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