The photoelectron spectrum and conformation of phenylphosphine and phenylarsine |
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Authors: | László Nyulászi Dénes Szieberth Gábor I Csonka József Reffy Joachim Heinicke Tamás Veszpremi |
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Institution: | (1) Department of Inorganic Chemistry, Technical University of Budapest, Szt. Gellért tér 4, H-1521 Budapest, Hungary;(2) Department of Chemistry, Ernst Moritz-Amdt University Greifswald, Greifswald, Germany |
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Abstract: | He(I) and He(II) photoelectron spectra of phenylphosphine and phenylarsine have been investigated and assigned. The rotational barrier of the phosphino group has been investigated at the MP2/6-31G(d,p)//MP2/6-31G(d,p) and HF/6-31G(d,p)//HF/6-31G(d,p) levels of theory, and that of the arsino group at the HF/6-31G(d,p)//6-31G(d,p) levels of theory. The rotational barrier of the two molecules is nearly the same. The energy difference between the two possible conformers of the molecules is low (1.5 kJ/mol at the MP2/6-31G(d,p) level of theory), allowing nearly free rotation about the P-C bond. The photoelectron spectrum cannot be interpreted by considering the most stable rotamer, but all possible conformers should be taken into account. The present interpretation is consistent with the smalln
p
- interaction concluded from other investigations. The rotational barrier ofo-phosphinophenol is significantly larger than for phenylphosphine, and the photoelectron spectrum of this compound can be interpreted by considering a single conformer, and no appreciable interaction between the -system of the ring and the phosphorus lone pair. |
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Keywords: | UV photoelectron spectroscopy ab initio quantum-chemical calculations phenylphosphine phenylarsine o-phosphinophenol o-arsinoaniline conformation rotational barrier |
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