TY - DATA T1 - To “Rollover” or Not? Stereoelectronically Guided C–H Functionalization Pathways from Rhodium–Abnormal NHC Intermediates PY - 2018/02/07 AU - Champak Dutta AU - Debasish Ghorai AU - Joyanta Choudhury UR - https://acs.figshare.com/articles/dataset/To_Rollover_or_Not_Stereoelectronically_Guided_C_H_Functionalization_Pathways_from_Rhodium_Abnormal_NHC_Intermediates/5866764 DO - 10.1021/acsomega.7b01846.s002 L4 - https://ndownloader.figshare.com/files/10420182 KW - pyridine-imidazolium substrates KW - chelating molecules KW - work addresses KW - Catalytic reactions KW - rollover KW - transition-metal complexes KW - NHC KW - nonrollover KW - pathway KW - activation KW - N-heterocyclic carbene KW - stereoelectronic demand KW - Rollover N2 - Rollover C–H activation with transition-metal complexes has been found to be a difficult but viable pathway to functionalize potentially chelating molecules, which are otherwise reluctant to react further. However, selective rollover or nonrollover C–H activation pathway depends on the stereoelectronic demand of the associated organometallic intermediate(s). The presented work addresses the above issue on abnormal N-heterocyclic carbene (NHC) platform. Catalytic reactions of pyridine-imidazolium substrates with internal alkynes have been selectively guided toward either rollover or nonrollover C–H functionalization route via fulfilling the steric and electronic demands of the relevant rhodium­(III)–abnormal NHC metallacyclic intermediates. ER -