An ab initio study of the electronic structure of the ground triplet and low-lying singlet states of formylnitrene, HCON and formylphosphinidene, HCOP

Mavridis, Aristides; Harrison, J.

doi:10.1021/ja00546a005

Cited by 21 publications

(12 citation statements)

References 3 publications

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“…A value of 4.3 kcal/mol 29 is obtained from photo‐detachment experiments on phenylnitrene (C6H5N:). Computational methods on formylnitrene (HCON:) yield a value of 10–35 kcal/mol 30–35. This energy difference is expected to be relatively insensitive to replacement of the hydrogen atom bound to carbon by other groups 34.…”

Section: Resultsmentioning

confidence: 99%

Theoretical investigation of the decomposition of acyl azides: Molecular orbital treatment

Abu‐Eittah¹,

Mohamed²,

Al-Omar³

2005

Int J of Quantum Chemistry

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ABSTRACT:The thermal decomposition of formyl, acetyl, and benzoyl azides to the corresponding isocyanate and nitrogen has been treated theoretically using ab initio molecular orbital calculations at the Møller-Plesset type 2 (MP2)(full)/6-31G* level. The reaction is stimulated by elongation of NON bond and is followed until the formation of the isocyanate and expulsion of nitrogen. The decomposition of formyl azide proved to be a concerted one-step reaction without the formation of a nitrene intermediate. In contrast, the conversion of both acetyl and benzoyl azides to the corresponding isocyanate and nitrogen is a two-step reaction, and a nitrene intermediate is formed. One transition state is located and identified during the course of the conversion of formyl azide, but two transition states are located and identified during the course of the conversion of acetyl and benzoyl azides. The thermodynamic functions, ⌬E r and ⌬H r , of the studied reactions are calculated. The results predict that the ease of conversion of the acyl azide to the isocyanate and nitrogen goes in the order: formyl azide Ͼ acetyl azide Ͼ benzoyl azide.

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Section: Resultsmentioning

confidence: 99%

Theoretical investigation of the decomposition of acyl azides: Molecular orbital treatment

Abu‐Eittah¹,

Mohamed²,

Al-Omar³

2005

Int J of Quantum Chemistry

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“…As in the case of carbene complexes, the bonding in terminal phosphinidenes and arsinidenes will depend inter alia on the electronic state of the main-group fragment. Theoretical studies indicate that a triplet ground state is favored for the parent phosphinidene, PH, and a variety of substituted phosphinidenes including PCH 3 , PC 6 H 5 , and PC(O)H . Experimentally, P(2,4,6-Me 3 C 6 H 2 ) has been matrix isolated and shown to possess a triplet ground state on the basis of ESR evidence and the triplet−singlet energy gap of PH has been measured in flowing afterglow experiments…”

Section: D-block Terminal Phosphinidenes and Arsinidenesmentioning

confidence: 99%

Terminal Phosphinidene and Heavier Congeneric Complexes. The Quest Is Over

Cowley

1997

Acc. Chem. Res.

201

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“…10,20,21 In contrast, formation of triplet carbonyl nitrenes was experimentally confirmed by EPR spectroscopy during the photolysis of alkoxycarbonyl azides (ROC(O)N 3 ), such as (4-acetylphenoxyl)carbonyl azide 11 and carbethoxy azide. 16 Quite recently, the ground-state multiplicities of fluorinated acylnitrenes, including FC(O)N, were computationally rationalized.…”

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confidence: 99%