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Substituents effects in phospha alkynes: A computational investigation
Author(s) -
Jayasuriya Keerthi
Publication year - 1992
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560440303
Subject(s) - substituent , electronegativity , lone pair , chemistry , triple bond , electrophile , alkyne , computational chemistry , bond order , polarizability , main group element , atom (system on chip) , bond length , crystallography , stereochemistry , transition metal , double bond , molecule , organic chemistry , crystal structure , computer science , embedded system , catalysis
Ab initio self‐consistent field ( SCF ) molecular orbital calculations were carried out at the MP 2/431 G * level to determine the effect of substituent groups, F, NH 2 , OH, CH 3 , CH 2 CH, and HCC—on the CP triple bond. Although there are considerable differences between the electronegativities of these substituent groups, a characteristic feature found in phospha alkyne derivatives is the weak sensitivity of the CP bond length to the substituent at the carbon atom. The molecular electrostatic potential analysis clearly reflects the strength of the electronegativity of these substituent groups and their ability to attract the polarizable charge from the CP triple bond. MEP analyzes further indicates that these derivatives of phospha alkynes are most likely to attract incoming electrophiles to the π‐electron region of the Ctriple bond. Transition metals are coordinated “sideways” with phospha alkynes, and in this configuration, the lone‐pair electrons of the phosphorus atom are unlikely to interact with the metal. © 1992 John Wiley & Sons, Inc.