Syntheses and Structures of <i>P</i>-Anilino-<i>P</i>-chalcogeno- and <i>P</i>-Anilino-<i>P</i>-iminodiazasilaphosphetidines and Their Group 12 and 13 Metal Compounds Dana C. Haagenson Daniel F. Moser Lothar Stahl Richard J. Staples 10.1021/ic010973f.s001 https://acs.figshare.com/articles/dataset/Syntheses_and_Structures_of_i_P_i_-Anilino-_i_P_i_-chalcogeno-_and_i_P_i_-Anilino-_i_P_i_-iminodiazasilaphosphetidines_and_Their_Group_12_and_13_Metal_Compounds/3604416 The <i>P</i>-anilino-<i>P</i>-chalcogeno(imino)diazasilaphosphetidines [Me<sub>2</sub>Si(μ-N<sup>t</sup>Bu)<sub>2</sub>PE(NHPh)] (E = O (<b>3</b>), S (<b>4</b>), Se (<b>5</b>), N-<i>p</i>-tolyl (<b>6</b>)) were synthesized by oxidizing the <i>P</i>-anilinodiazasilaphosphetidine [Me<sub>2</sub>Si(N<sup>t</sup>Bu)<sub>2</sub>P(NHPh)] (<b>2</b>) with cumene hydroperoxide, sulfur, selenium, and <i>p</i>-tolyl azide, respectively. The lithium salt of <b>4</b> reacted with thallium monochloride to produce {[Me<sub>2</sub>Si(μ-N<sup>t</sup>Bu)<sub>2</sub>PS(NPh)-κ<i>N</i>-κ<i>S</i>]Tl} (<b>7</b>), which features a two-coordinate thallium atom. Treatment of <b>4</b><b>−</b><b>6</b> with AlMe<sub>3</sub> gave the monoligand dimethylaluminum complexes {[Me<sub>2</sub>Si(μ-N<sup>t</sup>Bu)<sub>2</sub>PE(NPh)-κ<i>N</i>-κ<i>E</i>]AlMe<sub>2</sub>} (E = S (<b>8</b>), Se (<b>9</b>), N-<i>p</i>-tolyl (<b>10</b>)), respectively. In these complexes the aluminum atom is tetrahedrally coordinated by one chelating ligand and two methyl groups, as a single-crystal X-ray analysis of <b>8</b> showed. A 2 equiv amount of <b>4</b><b>−</b><b>6</b> reacted with diethylzinc to produce the homoleptic diligand complexes {[Me<sub>2</sub>Si(μ-N<sup>t</sup>Bu)<sub>2</sub>PE(NPh)-κ<i>N</i>-κ<i>E</i>]<sub>2</sub>Zn} (E = S (<b>11</b>), Se (<b>12</b>), N-<i>p</i>-tolyl (<b>13</b>)). A crystal-structure analysis of <b>11</b> revealed a linear tetraspirocycle with a tetrahedrally coordinated, central zinc atom. 2002-02-09 00:00:00 AlMe 3 thallium monochloride Group 12 Bu tetrahedrally Anilino lithium salt 13 Metal Compounds zinc atom methyl groups 2 Zn 2 equiv amount cumene hydroperoxide Si AlMe 2 Se chalcogeno chelating ligand tolyl azide aluminum atom complex analysis