10.1021/acs.inorgchem.5b00414.s004 Kuanysh Z. Kabytaev Kuanysh Z. Kabytaev Alexander V. Safronov Alexander V. Safronov Yulia V. Sevryugina Yulia V. Sevryugina Charles L. Barnes Charles L. Barnes Satish S. Jalisatgi Satish S. Jalisatgi M. Frederick Hawthorne M. Frederick Hawthorne Novel Synthetic Approach to Charge-Compensated Phosphonio-<i>nido</i>-Carboranes. Synthesis and Structural Characterization of Neutral Mono and Bis(Phosphonio) <i>nido</i>-<i>ortho</i>-Carboranes American Chemical Society 2015 PPh 3 multinuclear NMR spectroscopy Cs 2CO NaH Pd presence compounds 2 c tetrabutylammonium phosphine substitution product diiodo iodo 2015-04-20 00:00:00 Dataset https://acs.figshare.com/articles/dataset/Novel_Synthetic_Approach_to_Charge_Compensated_Phosphonio_i_nido_i_Carboranes_Synthesis_and_Structural_Characterization_of_Neutral_Mono_and_Bis_Phosphonio_i_nido_i_i_ortho_i_Carboranes/2175250 A number of monosubstituted <i>n</i>-(triphenylphosphonio)-7,8-dicarba-<i>nido</i>-undecaboranes (<b>2a</b>, <i>n</i> = 1; <b>2b</b>, <i>n</i> = 3; <b>2c</b>, <i>n</i> = 5; <b>2d</b>, <i>n</i> = 9) were prepared via a cross-coupling reaction between the tetrabutylammonium iodo-7,8-dicarba-<i>nido</i>-undecaborates (<b>1a</b>–<b>d</b>) and PPh<sub>3</sub> in the presence of a Pd­(PPh<sub>3</sub>)<sub>4</sub> catalyst. The substitution rate was found to depend on the iodine position in the carborane cage. Under similar conditions, the reaction of 5,6-diiodo- (<b>3</b>) and 9,11-diiodo-7,8-dicarba-<i>nido</i>-undecaborate (<b>5</b>) anions exclusively yielded the monosubstitution products 5-iodo-6-(triphenylphosphonio)-7,8-dicarba-<i>nido</i>-undecaborane (<b>4</b>) and 9-iodo-11-(triphenylphosphonio)-7,8-dicarba-<i>nido</i>-undecaborane (<b>6</b>), respectively. The reaction of tetrabutylammonium 6,9-diiodo-7,8-dicarba-<i>nido</i>-undecaborate (<b>7</b>) exclusively produced the phosphine substitution product in the open face of the <i>nido</i>-carborane, 6-iodo-9-triphenylphosphonio-7,8-dicarba-<i>nido</i>-undecaborane (<b>8</b>). The addition of a base (Cs<sub>2</sub>CO<sub>3</sub>, NaH) to the reactions of <b>3</b> and <b>5</b> with PPh<sub>3</sub> afforded the corresponding bis­(triphenylphosphonio)-7,8-dicarba-<i>nido</i>-undecaboranes, <b>9</b> and <b>10</b>. Compound <b>10</b> was also prepared from <b>6</b> using the general procedure. The reaction of the triiodocarborane tetrabutylammonium 5,6,9-triiodo-7,8-dicarba-<i>nido</i>-undecaborate (<b>11</b>) with excess PPh<sub>3</sub> in the presence of Cs<sub>2</sub>CO<sub>3</sub> and Pd­(PPh<sub>3</sub>)<sub>4</sub> only produced neutral 5-iodo-6,9-bis­(triphenylphosphonio)-7,8-dicarba-<i>nido</i>-undecaborane (<b>12</b>); no positively charged tris­(phosphonio) species formed. The compositions of all prepared compounds were determined by multinuclear NMR spectroscopy and high-resolution mass spectrometry. The structures of compounds <b>2c</b>, <b>6</b>, <b>8</b>, <b>9</b>, and <b>12</b> were established by the X-ray diffraction analysis of single crystals.