The M06 density functional was utilized to study the interactions of substituted and unsubstituted alkenes and alkynes to Au(I)Cl and Pd(II)(PH3)2Cl+ complexes. Equilibrium geometries and energies of coordination of these complexes were determined. A strong correlation (R2 = 0.90) was found for coordination energy of 1,4 disubstituted 2-butyne with Hammett substituent (s) constants. Coordination energy was found to increase for symmetric alkynes as chain length increased until 8-octyne. Unsubstituted alkenes were found to coordinate approximately 10 kcal/mol stronger than alkynes. Electron withdrawing substituents could lower the energy of coordination of an alkene below that of an unsubstituted alkyne. The Natural Bond Orbital analysis was performed to determine substituent effects on filled d - p* and empty d - p interactions between the metal and alkene or alkyne.

Substituent effects on coordination energies of alkenes and alkynes to Au and Pd complexes

246th National Meeting (2013)

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