A computational study based on density functional theory provided insight into the details of H2 activation on complex [(�-pdt){Fe(CO)3}{Fe(CO)(PNP)}] (1+  , pdt = propane-1,3-dithiolate, PNP = Ph2PCH2N(nPr)CH2PPh2)1.Figure 1  . Profile of the calculated relative G for H2 activation on 1  +in dichloromethame. The relative Gibbs free energies are given in kcal/mol.we performed a computational study of the mechanism for the reaction of [1  ]+ and H2 to afford [1  H�HN]2+ (Figure 1). The favorable reaction path starts from rotation of the semi-bridging CO to an apical position with a free energy barrier of 14.60 kcal mol-1 via ts-[1  ]+. The intermediate [1  -terminal CO]+ is then capable of binding H2 from down site to form [1  (?2-H2]+ via ts-[1  (?2-H2]+, overcoming a barrier of 8.91 kcal mol-1. With the involvement of internal amine N, the calculated activation free energy associated with heterolytic cleavage of H�H bond in [1  (?2-H2)]+ via ts-[1-  H�H]+ is only 4.69 kcal mol-1. The thereby gener-ated [1  H�HN]+ converts to [1  H�HN]2+ by one electron oxidation for which a potential of -0.70 V vs Fc+/0 was calculated. The total free energy barrier for this H2-activation pathway is 22.29 kcal mol-1. The results show that the inclusion of the internal amine base in [1  ]+  is important for efficient H2activation.References Ning Wang, Mei Wang*, Ying Wang  , Dehua Zheng, Hongxian Han, M�rten S.G. Ahlquist, Licheng, Sun*. J. Am. Chem.Soc. 2013  , 135, 13688-13691.

Theoretical study on H2 activation on FeIIFeI complex 1+

248th National Meeting (2014)

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