Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2 center dot+ (E=N, P, As)

Letzel M, Grützmacher H-F, Stein D, Grützmacher H (2008)
DALTON TRANSACTIONS (25): 3282-3291.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
pnictogens C6H5EH2, E = N ( 1), P ( 2), and As ( 3), the mass spectrometric reactions of phenyl phosphane 2 have been re-investigated by D-labeling and by using methods of tandem mass spectrometry. The 70 eV mass spectrum of 2 shows the base peak for ion [ M- 2H](center dot+) and significant peaks for ions [ M-H](+), [ M-( 2C, 3H)](+), [ M- PH](center dot+), and [ M-( C, P, 2H)](+). Metastable 2(center dot+) fragments exclusively by loss of H-2, and the investigation of deuterated 2-d(2) shows that excessive H/D migrations occur before fragmentation. Other significant fragment ions in the mass spectrum of 2 arise by losses of C2H2, P, or HCP from the ion [M-H](+). This mass spectrometric behavior puts the radical cation 2(center dot+) in between the fragmentation reactions of aniline radical cation 1(center dot+) ( loss of H and subsequent losses of C2H2, or HCN) and phenyl arsane radical cation 3(center dot+) ( elimination of H2 and loss of As from ion [ M- H]+). The fragmentation mechanisms of the radical cations 1(center dot+)-3(center dot+) and of related ions were analyzed by calculations of the enthalpy of relevant species at the stationary points of the minimum enthalpy reaction pathways using the DFT hybrid functionals UBHLYP/6-311+G(2d,p)// UBHLYP/ 6- 311+ G( d). The results show that, in contrast to ionized aniline 1(center dot+), the reactions of the derivatives 2(center dot+) and 3(center dot+) of the heavier main group elements P and As are characterized by an easy elimination of H2 via a reductive elimination of group C6H5- E ( E = P, As) and by a special stability of bicyclic isomers of 2(center dot+) and 3(center dot+). Thus, while 1(center dot+) rearranges by ring expansion and formation an 7-aza-tropylium cation by loss of H center dot, the increased stability of bicyclic intermediates in the rearrangement of 2 center dot+ and in particular of 3(center dot+) results in separate rearrangement pathways. The origin of these effects is the more extended and diffuse nature of the 3p and 4p AO of P and As.
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DALTON TRANSACTIONS
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25
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3282-3291
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Letzel M, Grützmacher H-F, Stein D, Grützmacher H. Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2 center dot+ (E=N, P, As). DALTON TRANSACTIONS. 2008;(25):3282-3291.
Letzel, M., Grützmacher, H. - F., Stein, D., & Grützmacher, H. (2008). Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2 center dot+ (E=N, P, As). DALTON TRANSACTIONS(25), 3282-3291. doi:10.1039/b801970c
Letzel, M., Grützmacher, H. - F., Stein, D., and Grützmacher, H. (2008). Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2 center dot+ (E=N, P, As). DALTON TRANSACTIONS, 3282-3291.
Letzel, M., et al., 2008. Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2 center dot+ (E=N, P, As). DALTON TRANSACTIONS, (25), p 3282-3291.
M. Letzel, et al., “Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2 center dot+ (E=N, P, As)”, DALTON TRANSACTIONS, 2008, pp. 3282-3291.
Letzel, M., Grützmacher, H.-F., Stein, D., Grützmacher, H.: Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2 center dot+ (E=N, P, As). DALTON TRANSACTIONS. 3282-3291 (2008).
Letzel, Matthias, Grützmacher, Hans-Friedrich, Stein, Daniel, and Grützmacher, Hansjörg. “Trends in the reactions of gaseous phenyl pnictogen radical cations C6H5EH2 center dot+ (E=N, P, As)”. DALTON TRANSACTIONS 25 (2008): 3282-3291.

17 References

Daten bereitgestellt von Europe PubMed Central.


Letzel, Dalton Trans. (), 2006

Kirchhoff, Eur. J. Mass Spectrom. 12(), 2007

Grützmacher, Organometallics 20(), 2001

Mohr, J. Phys. Chem. A 101(), 1997

Momigny, Bull. Soc. R. Sci. Liège 22(), 1953

Rylander, J. Am. Chem. Soc. 85(), 1963

Robertson, J. Am. Chem. Soc. 90(), 1968

Hammerum, Adv. Mass Spectrom. 7B(), 1976

Lifshitz, Chem. Phys. Lett. 95(), 1983

Burgers, Chem. Phy. Lett. 102(), 1983

Atmani, Bull. Soc. Chim. Belg. 91(), 1982

Zimmerman, Chem. Phys. Lett. 147(), 1988

Lifshitz, Acc. Chem. Res. 27(), 1994

Zeeh, Tetrahedron Lett. 10(), 1969

Kirchhoff, Int. J. Mass Spectrom. 255/256(), 2006

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