Vicente, José Gil-Rubio, Juan Bautista, Delia Sironi, Angelo Masciocchi, Norberto Synthesis and Reactivity of Fluoro Complexes:  Part 2. Rhodium(I) Fluoro Complexes with Alkene and Phosphine Ligands. Synthesis of the First Isolated Rhodium(I) Bifluoride Complexes. Structure of [Rh<sub>3</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(COD)<sub>3</sub>](HF<sub>2</sub>) by X-ray Powder Diffraction The reaction between [Rh(μ-OH)(COD)]<sub>2</sub> (COD = 1,5-cyclooctadiene) and 73% HF in THF gives [Rh<sub>3</sub>(μ<sub>3</sub>-OH)<sub>2</sub>(COD)<sub>3</sub>](HF<sub>2</sub>) (<b>1</b>). Its crystal structure, determined by ab initio X-ray powder diffraction methods (from conventional laboratory data), contains complex trimetallic cations linked together in 1D chains by a μ<sub>3</sub>-OH···F−H−F···HO-μ<sub>3</sub> sequence of strong hydrogen bonds. The complex [Rh(μ-F)(COE)<sub>2</sub>]<sub>2</sub> (COE = cyclooctene; <b>2</b>), prepared by reacting [Rh(μ-OH)(COE)<sub>2</sub>]<sub>2</sub> with NEt<sub>3</sub>·3HF (3:2), has been characterized. Complex <b>1 </b>reacts with PR<sub>3</sub> (1:3) to give [RhF(COD)(PR<sub>3</sub>)] [R = Ph (<b>3</b>), C<sub>6</sub>H<sub>4</sub>OMe-4 (<b>4</b>), <i><sup>i</sup></i><sup></sup>Pr (<b>5</b>), Cy (<b>6</b>)] that can be prepared directly by reacting [Rh(μ-OH)(COD)]<sub>2</sub> with 73% HF and PR<sub>3</sub> (1:2:2). The reactions of <b>1</b> with PPh<sub>3</sub> or Et<sub>3</sub>P have been studied by NMR spectroscopy at different molar ratios. Complexes [RhF(PEt<sub>3</sub>)<sub>3</sub>] (<b>7</b>), [RhF(COD)(PEt<sub>3</sub>)] (<b>8</b>), and [RhF(PPh<sub>3</sub>)<sub>3</sub>] (<b>9</b>) have been detected. The complex [Rh(F)(NBD)(<i><sup>i</sup></i><sup></sup>Pr<sub>3</sub>P)] (NBD = norbornadiene; <b>10</b>) was prepared by the sequential treatment of [Rh(μ-OMe)(NBD)]<sub>2</sub> with 1 equiv of NEt<sub>3</sub>·3HF and <i><sup>i</sup></i><sup></sup>Pr<sub>3</sub>P. The first isolated bifluoride rhodium(I) complexes [Rh(FHF)(COD)(PR<sub>3</sub>)] [R = Ph (<b>11</b>), <i><sup>i</sup></i><sup></sup>Pr (<b>12</b>), Cy (<b>13)</b>], obtained by reacting fluoro complexes <b>3</b>, <b>5</b>, and <b>6</b> with NEt<sub>3</sub>·3HF (3:1), have been characterized. The crystal structures of <b>3</b> and <b>11</b> have been determined. molar ratios;Rh;PPh 3;THF;OH;HF;1 D chains;PR;fluoro complexes 3;Complexe;Complex 1;μ 3;COE;trimetallic cations;NBD;sequential treatment;Et 3 P;crystal structure;Phosphine Ligands;crystal structures;RhF;NMR spectroscopy;hydrogen bonds;i Pr 3 P;1 equiv 2004-09-06
    https://acs.figshare.com/articles/dataset/Synthesis_and_Reactivity_of_Fluoro_Complexes_Part_2_Rhodium_I_Fluoro_Complexes_with_Alkene_and_Phosphine_Ligands_Synthesis_of_the_First_Isolated_Rhodium_I_Bifluoride_Complexes_Structure_of_Rh_sub_3_sub_sub_3_sub_OH_sub_2_sub_COD_sub_3_sub_HF_sub_2_sub_by_/3326113
10.1021/ic049585e.s001