“Nitrogen inversion”的意思、由来-开放百科全书

In chemistry, nitrogen inversion is a fluxional process in nitrogen and amines, whereby the molecule "turns inside out". It is a rapid oscillation of the nitrogen atom and substituents, the nitrogen "moving" through the plane formed by the substituents (although the substituents also move - in the other direction);^[1] the molecule passing through a planar transition state.^[2] For a compound that would otherwise be chiral due to a nitrogen stereocenter, nitrogen inversion provides a low energy pathway for racemization, usually making chiral resolution impossible.^[3]

Nitrogen inversion is one case of the more general phenomenon of pyramidal inversion, which applies to carbanions, phosphines, arsines, stibines, and sulfoxides.^[4]^[5]

Energy barrier

The ammonia interconversion is rapid at room temperature, inverting 30 billion times per second. Two factors contribute to the rapidity of the inversion: a low energy barrier (24.2 kJ/mol; 5.8 kcal/mol) and a narrow width of the barrier itself{{clarify|date=November 2014}}, which allows for frequent quantum tunnelling (see below). In contrast, phosphine (PH₃) inverts very slowly at room temperature (energy barrier: 132 kJ/mol).^[6]

Quantum effects

Ammonia exhibits a quantum tunnelling due to a narrow tunneling barrier,^[7] and not due to thermal excitation. Superposition of two states leads to energy level splitting, which is used in ammonia masers.

Examples

The inversion of ammonia was first detected by microwave spectroscopy in 1934.^[8]

In one study the inversion in an aziridine was slowed by a factor of 50 by placing the nitrogen atom in the vicinity of a phenolic alcohol group compared to the oxidized hydroquinone.^[9]

The system interconverts by oxidation by oxygen and reduction by sodium dithionite.

References

1. ^{{Greenwood&Earnshaw2nd|page=423}}
2. ^{{ cite journal | author = J. M. Lehn | authorlink = Jean-Marie Lehn | title = Nitrogen Inversion: Experiment and Theory | journal = Fortschr. Chem. Forsch. | year = 1970 | volume = 15 | pages = 311-377 | doi = 10.1007/BFb0050820 }}
3. ^{{March6th|pages=142-145}}
4. ^{{ cite journal | authors = Arvi Rauk, Leland C. Allen, Kurt Mislow | title = Pyramidal Inversion | journal = Angew. Chem. Int. Ed. | year = 1970 | volume = 9 | pages = 400-414 | doi = 10.1002/anie.197004001 }}
5. ^{{GoldBookRef|file=P04956|title=Pyramidal inversion}}
6. ^{{cite journal | last1 = Kölmel | first1 = C. | last2 = Ochsenfeld | first2 = C. | last3 = Ahlrichs | first3 = R. | year = 1991 | title = An ab initio investigation of structure and inversion barrier of triisopropylamine and related amines and phosphines | url = | journal = Theor. Chim. Acta. | volume = 82 | issue = 3-4| pages = 271–284 | doi = 10.1007/BF01113258 }}
7. ^{{cite book | last = Feynman | first = Richard P. | authorlink = Richard Feynman |author2=Robert Leighton |author3=Matthew Sands | title = The Feynman Lectures on Physics |volume=Volume III |chapter=The Hamiltonian matrix | publisher = Addison-Wesley | year = 1965 | location = Massachusetts, USA | isbn = 0-201-02118-8}}
8. ^{{cite journal|last=Cleeton|first=C.E.|author2=Williams, N.H. |title=Electromagnetic waves of 1.1 cm wave-length and the absorption spectrum of ammonia|journal=Physical Review|year=1934|volume=45|pages=234–237|doi=10.1103/PhysRev.45.234|bibcode = 1934PhRv...45..234C|issue=4 }}
9. ^Control of Pyramidal Inversion Rates by Redox Switching Mark W. Davies, Michael Shipman, James H. R. Tucker, and Tiffany R. Walsh J. Am. Chem. Soc.; 2006; 128(44) pp. 14260–14261; (Communication) {{DOI|10.1021/ja065325f}}