A Model Study on Molecular Properties and Mechanistic Investigations of P=C=E-14 Molecules

作者：Li Ming Chung; Shih Tsung Wei; Li Yu Chi; Ma Jia Ying; Su Ming Der^*

来源：European Journal of Inorganic Chemistry, 2015, 2015(10): 1795-1803.

DOI：10.1002/ejic.201500037

• Bond theory
• Density functional calculations
• Cycloaddition
• Allenes
• Chalcogens

The bonding properties and the potential energy surfaces for the chemical reactions of heteroallenic compounds with a -P=C=E-14< pattern are studied by using density functional theory (M06-2X/Def2-SVPD). Five Mes*P=C=E-14(tBu)Tip species, for which E-14 = C, Si, Ge, Sn, and Pb, were used as model reactants in this work. The theoretical evidence shows that Mes*P=C=E-14(tBu)Tip molecules have both P=C and C=E-14 double bonds. Four types of chemical reaction - water addition, acetylene [3+2] cycloaddition, ketone [2+2] cycloaddition, and selenium [1+2] cycloaddition - have been used to study the reactive activity of these group 14 heteroallenic molecules. This theoretical work predicts that the heavier the group 14 element (E-14) in the heteroallenic -P=C=E-14< compounds, the smaller is its singlet-triplet energy splitting, the lower is its activation barrier, and the more rapid are its chemical reactions with various chemical species. As a result, this theoretical investigation shows that the relative reactivity of -P=C=E-14< increases in the order: -P=C=C<, -P=C=Si<, -P=C=Ge<, -P=C=Sn<, and -P=C=Pb<.

• 出版日期2015-4