ISSN:
1572-9001
Keywords:
UV photoelectron spectroscopy
;
ab initio quantum-chemical calculations
;
phenylphosphine
;
phenylarsine
;
o-phosphinophenol
;
o-arsinoaniline
;
conformation
;
rotational barrier
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
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 - π 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 π-system of the ring and the phosphorus lone pair.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF02263522
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