Aharonovich, Sinai Botoshanski, Mark Eisen, Moris S. Synthesis of Lithium <i>N</i>-pentafluorophenyl, <i>N</i>′-trimethylsilyl 2-Pyridylamidinate and Its Cyclization to Lithium Tetrafluoro-2-(2-pyridyl)benzimidazolate via a Me<sub>3</sub>SiF Elimination. Coordination Chemistry, Reactivity, and Mechanism When <i>N</i>-trimethylsilylpentafluoro aniline reacts with BuLi in the presence of THF or TMEDA, the corresponding THF (<b>2</b>) or TMEDA (<b>4</b>) lithium anilides are obtained. Complex <b>4</b> is monomeric in the solid state, with a distorted trigonal pyramidal coordination geometry at the lithium center. The strong C−F→Li interaction in this complex is also accompanied by the elongation of the C−F bond. Mild heating of complex <b>4</b> with 2-cyanopyridine results in rapid evolution of Me<sub>3</sub>SiF to quantitatively yield the tetrafluoro-2-(2-pyridyl)benzimidazolate lithium complex (<b>6</b>). From the reaction mixture of complex <b>4</b> the asymmetric <i>N</i>-trimethylsilyl, <i>N</i>′-pentafluorophenyl-2-pyridylamidinate lithium complex (<b>5</b>) was isolated as a dormant intermediate. Complex <b>5</b> possesses several unusual bonding features with the most notably being a very short Si−N bond length and a rare κ<sup>1</sup>-Z-syn amidinate bonding mode. A mechanism that includes silicon assisted C−F bond activation is proposed for the cyclization reaction based on the structural parameters of complexes <b>5</b> and <b>6</b>, and on <sup>1</sup>H, <sup>19</sup>F, and <sup>13</sup>C NMR studies. THF;bond;reaction mixture;complexes 5;3SiF Elimination;Mild heating;Complex 4;19 F;Coordination Chemistry;TMEDA;Complex 5;cyclization reaction;Lithium;13 C NMR studies;coordination geometry;1 H;lithium center 2009-06-15
    https://acs.figshare.com/articles/dataset/Synthesis_of_Lithium_i_N_i_pentafluorophenyl_i_N_i_trimethylsilyl_2_Pyridylamidinate_and_Its_Cyclization_to_Lithium_Tetrafluoro_2_2_pyridyl_benzimidazolate_via_a_Me_sub_3_sub_SiF_Elimination_Coordination_Chemistry_Reactivity_and_Mechanism/2850226
10.1021/ic9002065.s001