10.1021/ja0547580.s001 Amy Walstrom Amy Walstrom Maren Pink Maren Pink Nikolai P. Tsvetkov Nikolai P. Tsvetkov Hongjun Fan Hongjun Fan Michael Ingleson Michael Ingleson Kenneth G. Caulton Kenneth G. Caulton N<sub>2</sub> Provides Insight into the Mechanism of H−C(sp<sup>3</sup>) Bond Cleavage American Chemical Society 2005 benzene N 2 product Bond Cleavage Exchange HN N 2 Ru II amine ligand PNP nitrogen Bu N 2 Provides Insight CH DFT results OSO 2 CF 3 formation energy bond 2005-12-07 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/N_sub_2_sub_Provides_Insight_into_the_Mechanism_of_H_C_sp_sup_3_sup_Bond_Cleavage/3253201 Exchange of deuterium in <i>d</i><sub>6</sub>-benzene with all C−H sites in (PNP)Ru(OTf), where PNP is N(SiMe<sub>2</sub>CH<sub>2</sub>P<sup>t</sup>Bu<sub>2</sub>)<sub>2</sub> and OTf is OSO<sub>2</sub>CF<sub>3</sub>, is rapid at 22 °C. Although intact planar triplet (PNP)Ru(OTf) binds N<sub>2</sub> only very weakly, these reagents are observed to react rapidly to give a diamagnetic 1:1 adduct whose structure has one <sup>t</sup>Bu C−H bond cleaved:  the carbon binds to Ru but the hydrogen is on the PNP nitrogen, creating a secondary amine ligand bound to Ru<sup>II</sup>. It is suggested that the benzene C−D cleavage and the N<sub>2</sub> product of <sup>t</sup>Bu C−H bond heterolysis both derive from a common intermediate, [HN(SiMe<sub>2</sub>CH<sub>2</sub>P<sup>t</sup>Bu<sub>2</sub>)(SiMe<sub>2</sub>CH<sub>2</sub>P<sup>t</sup>BuCMe<sub>2</sub>CH<sub>2</sub>)] Ru(OTf); the formation energy and structure of this species are discussed on the basis of DFT results.