Density functional studies of influences of Ni triad metals and solvents on oxidative addition of Mel to [M(Ch3)2(NH3)2] complexes and C–C reductive elimination from [M(CH3)3(NH3)2I] complexes
Hosseini, FN and Ariafard, A and Rashidi, M and Azimi, G and Nabavizadeh, SM, Density functional studies of influences of Ni triad metals and solvents on oxidative addition of Mel to [M(Ch3)2(NH3)2] complexes and C–C reductive elimination from [M(CH3)3(NH3)2I] complexes, Journal of Organometallic Chemistry, 696, (21) pp. 3351-3358. ISSN 0022-328X (2011) [Refereed Article]
Three metal square planar complexes of the type [M(CH3)2(NH3)2] (M = Ni, Pd, Pt), with a systematic variation in the metals, are chosen to investigating their SN2-type oxidative addition reactions with methyl iodide by using the B3LYP levels of theory. The oxidative addition was found to take place via a transition state with a nearly linear arrangement of the I–CH3–M moiety. Solvation effects in these oxidative addition reactions were also investigated. Considering the nature of the metal centre and solvation effects, the following conclusions emerge: (i) addition of MeI is exothermic for all three metals, and Pt is predicted to react with a much lower barrier than either Pd or Ni. The results describe that the MeI addition would be expected to be more favourable with the complex bearing the third-row metal (platinum) as compared to the other triad metals, nickel or palladium, in which case a more strongly bound MeI adduct is formed with a lower activation barriers and the reaction being more exothermic; (ii) the reaction is very difficult to occur in low polar solvents, such as benzene, due to the high barrier which is induced by dissociation of iodide anion from methyl group, but the reaction easily occurs in polar solvents, such as acetonitrile; this is attributed to the ability of polar solvents to solvate and therefore stabilize the related polar intermediate ion pair. Ethane reductive elimination from the M(VI) complexes fac-[M(CH3)3(NH3)2I] were also studied, indicating that the Ni(IV) and Pd(IV) complexes are very prone to undergo the reductive elimination while the Pt(IV) analogous is less reactive towards the reductive elimination. The results indicate that in contrast to the Me–Me reductive elimination, the SN2 oxidative addition reaction of MeI to M(II) is much less sensitive to the nature of the metal centre, suggesting that the nucleophilicity of M(II) in [M(CH3)2(NH3)2] does not change significantly as one moves from M = Ni to Pt.
oxidative addition, reductive elimination, Ni triad metals, DFT calculation