**The Mechanisms for the Oxidative Addition of Imidazolium Salts to a Group 9 Transition Metal Atom (Co0, Rh0, and Ir0) and a Group 10 Transition Metal Atom (Ni0, Pd0, and Pt0): A Theoretical Study**

Hsin-Yi Liao, Jia-Syun Lu and Ming-Der Su

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/67567

#### **Abstract**

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152 Descriptive Inorganic Chemistry Researches of Metal Compounds

The potential energy surfaces of the oxidative addition reactions, L2 M + imidazolium cation → product and CpM′L + imidazolium cation → product (M = Ni, Pd, Pt; M′ = Co, Rh, Ir; Cp = η<sup>5</sup> -C5 H5 ; L = 1,3-aryl-N-heterocyclic carbene (NHC), aryl = 2,4,6-trimethylphenyl), are studied at the M06-L/Def2-SVP level of theory. The theoretical findings show that the singlet-triplet splitting (∆*E*st = *E*triplet − *E*singlet) for the L2 M and CpM′L species can be used to predict the reactivity for their oxidative additions. That is to say, current theoretical evidence suggests that both a 14-electron L2 M complex and a 16-electron CpM′Lcomplex with a better electron-donating ligand L (such as NHC) result in a reduced ∆*E*st value and facilitate the oxidative addition to the saturated C─H bond. The theoretical results for this study are in good agreement with the obtainable experimental results and allow a number of predictions to be made.

**Keywords:** oxidative addition reactions, group 9 elements, group 10 elements, imidazolium and density functional theory
