The Vanadium(V) Oxoazides [VO(N3)3], [(bipy)VO(N3)3], and [VO(N3)5]2−

Haiges, Ralf; Vasiliu, Monica; Dixon, David A.

doi:10.1002/ange.201503985

Cited by 11 publications

(1 citation statement)

References 38 publications

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“…The main step to design promising energetic materials is to acquire an effective energetic building unit, which could be further assembled and modied by energetic functional groups. [1][2][3][4][5][6][7][8][9][10] Obviously, excellent energetic units played a crucial role in the development of energetic materials.…”

Section: Introductionmentioning

confidence: 99%

Monocyclic and bicyclic CO₄: how stable are they?

Gao

Petris

et al. 2015

RSC Adv.

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Seeking promising molecular species with huge energy release and significant kinetic stability continues to be a hot topic and a great challenge in the field of high-energy density materials (HEDMs). CO 4 is the first high-order carboxide that has the potential as an energetic molecule. However, the intrinsic kinetic stability of its two most studied energy-rich isomers, i.e., 1 1 (monocyclic) and 1 2 (bicyclic), has remained quite unclear in spite of numerous studies. This has greatly hindered the quantitative stability assessment of 1 1 and 1 2 under various conditions as well as the justification of their prospect as energetic candidates. In this work, for the first time we report the rate-determining transition states associated with the CO 2elimination from 1 1 and 1 2. The thermodynamics of 1 1 and 1 2 was described using G3B3, CBS-QB3, G4, W1BD, CCSD(T)/CBS and CASPT2/CBS, while the kinetic stability was analyzed based on brokensymmetry UCCSD(T)/CBS and CASPT2/CBS single-point energy calculations on UB3LYP geometries. The rate-determining barriers for the dissociation of 1 1 and 1 2 into CO 2 + 1 O 2 at 298 K were found to amount to 28.7 and 14.7 kcal mol À1 at the CASPT2(18e,12o)/CBS level of theory, and 23.5 and 21.1 kcal mol À1 at the UCCSD(T)/CBS level of theory, respectively. 1 1 is a kinetically stable energetic molecule, which releases 45.2 kcal mol À1 upon dissociation into CO 2 + 1 O 2 at the CASPT2(18e,12o)/CBS level and 38.9 kcal mol À1 at the UCCSD(T)/CBS level, and could serve as a rigid energetic building block for larger oxocarbons. The bicyclic 1 2 releases much higher energy, 79.3 kcal mol À1 at the CASPT2(18e,12o)/CBS level and 73.4 kcal mol À1 at the CASPT2-corrected UCCSD(T)/CBS level whereas the barrier for dissociation is lower than that of monocyclic 1 1.

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Section: Introductionmentioning

confidence: 99%

Monocyclic and bicyclic CO₄: how stable are they?

Gao

Petris

et al. 2015

RSC Adv.

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Die Molybdän(V)‐ und Wolfram(VI)‐oxoazide [MoO(N₃)₃], [MoO(N₃)₃⋅2 CH₃CN], [(bipy)MoO(N₃)₃], [MoO(N₃)₅]²⁻, [WO(N₃)₄] und [WO(N₃)₄⋅CH₃CN]

et al. 2015

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Eine Serie neuartiger Molybdän(V)-und Wolfram-(VI)-oxoazide wurdea usgehend von [MOF 4 ]( M= Mo,W ) und Me 3 SiN 3 synthetisiert. Während [WO(N 3 ) 4 ]durch Fluorid-Azid-Austauschinder Umsetzung von Me 3 SiN 3 mit [WOF 4 ]in SO 2 -Lçsung erhalten wurde,r esultierte die Reaktion mit MoOF 4 in einer Reduktion von Mo VI zu Mo V unter Bildung von [MoO(N 3 ) 3 ]. Entsprechende Umsetzungen in Acetonitrillçsung führten zur Isolierung der Addukte [MoO-(N 3 ) 3 ·2 CH 3 CN] und [WO(N 3 ) 4 ·CH 3 CN].[ (bipy)MoO(N 3 ) 3 ] und [PPh 4 ] 2 [MoO(N 3 ) 5 ]k onnten nacha nschließenden Umsetzungen von [MoO(N 3 ) 3 ]mit 2,2'-Bipyridin bzw.[PPh 4 ][N 3 ] isoliert werden. Die Molybdän(V)-und Wolfram(VI)-oxoazide wurden schwingungsspektroskopisch, bezüglichi hrer Empfindlichkeit gegenüber Schlag,Reibung und Erhitzen,und im Fall von [WO(N 3 ) 4 ·CH 3 CN],[ (bipy)MoO(N 3 ) 3 ]u nd [PPh 4 ] 2 [MoO(N 3 ) 5 ]a uchd urch Kristallstrukturanalysen charakterisiert.

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Ralf Haiges

2015

Angewandte Chemie

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The Vanadium(V) Oxoazides [VO(N₃)₃], [(bipy)VO(N₃)₃], and [VO(N₃)₅]²⁻

Cited by 11 publications

References 38 publications

Monocyclic and bicyclic CO₄: how stable are they?

Monocyclic and bicyclic CO₄: how stable are they?

Die Molybdän(V)‐ und Wolfram(VI)‐oxoazide [MoO(N₃)₃], [MoO(N₃)₃⋅2 CH₃CN], [(bipy)MoO(N₃)₃], [MoO(N₃)₅]²⁻, [WO(N₃)₄] und [WO(N₃)₄⋅CH₃CN]

Ralf Haiges

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The Vanadium(V) Oxoazides [VO(N3)3], [(bipy)VO(N3)3], and [VO(N3)5]2−

Cited by 11 publications

References 38 publications

Monocyclic and bicyclic CO4: how stable are they?

Monocyclic and bicyclic CO4: how stable are they?

Die Molybdän(V)‐ und Wolfram(VI)‐oxoazide [MoO(N3)3], [MoO(N3)3⋅2 CH3CN], [(bipy)MoO(N3)3], [MoO(N3)5]2−, [WO(N3)4] und [WO(N3)4⋅CH3CN]

Ralf Haiges

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The Vanadium(V) Oxoazides [VO(N₃)₃], [(bipy)VO(N₃)₃], and [VO(N₃)₅]²⁻

Monocyclic and bicyclic CO₄: how stable are they?

Monocyclic and bicyclic CO₄: how stable are they?

Die Molybdän(V)‐ und Wolfram(VI)‐oxoazide [MoO(N₃)₃], [MoO(N₃)₃⋅2 CH₃CN], [(bipy)MoO(N₃)₃], [MoO(N₃)₅]²⁻, [WO(N₃)₄] und [WO(N₃)₄⋅CH₃CN]