10.1021/om1010935.s001 Fengying Zhou Fengying Zhou Miaoshui Lin Miaoshui Lin Lei Li Lei Li Xueqing Zhang Xueqing Zhang Zhou Chen Zhou Chen Yahong Li Yahong Li Yang Zhao Yang Zhao Jin Wu Jin Wu Guimin Qian Guimin Qian Bin Hu Bin Hu Wu Li Wu Li Heterobimetallic Samarium(III) and Titanium(IV) Complexes with Bifunctional Catalytic Properties American Chemical Society 2011 titanium amido Ti samarium atom pyrrolyl ring Bifunctional Catalytic PropertiesReaction polymerization reactions H 3bptd ligand titanium center Sm 1 equiv Complexe coordination number 2011-03-28 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Heterobimetallic_Samarium_III_and_Titanium_IV_Complexes_with_Bifunctional_Catalytic_Properties/2676862 Reaction of the bis-ligand-chelated samarium complex [Sm(Hbptd)(H<sub>2</sub>bptd)] (<b>1</b>; H<sub>3</sub>bptd =1,9-bis(2-pyrrolyl)-2,5,8-triazanona-1,8-diene), in which a pyrrolyl ring is dangling and metal-free, with Ti(NMe<sub>2</sub>)<sub>4</sub> yielded the heterometallic complex [Sm(Hbptd)(THF)(bptd)Ti(NMe<sub>2</sub>)<sub>2</sub>] (<b>2</b>). Treatment of the H<sub>3</sub>bptd ligand with 1 equiv of Ti(NMe<sub>2</sub>)<sub>4</sub> gave the titanium amido complex [Ti(bptd)(NMe<sub>2</sub>)] (<b>3</b>). Complexes <b>2</b> and <b>3</b> were able to catalyze the hydroamination of phenylacetylene with 2,4-dichloroaniline and 4-methoxyaniline, and high regioselectivities were observed for the two amines. Both <b>1</b> and <b>2</b> were active catalysts for the ring-opening polymerization of ε-caprolactone. <b>2</b> showed higher activity for the polymerization reactions, due to a decrease in the coordination number of the samarium atom (from 9 in <b>1</b> to 8 in <b>2</b>) by sharing its ligand with the titanium center.