Fernández, Damián García-Seijo, M. Inés Kégl, Tamás Petőcz, György Kollár, László García-Fernández, M. Esther Preparation and Structural Characterization of Ionic Five-Coordinate Palladium(II) and Platinum(II) Complexes of the Ligand Tris[2-(diphenylphosphino)ethyl]phosphine. Insertion of SnCl<sub>2</sub> into M−Cl Bonds (M = Pd, Pt) and Hydroformylation Activity of the Pt−SnCl<sub>3</sub> Systems The five-coordinate palladium(II) and platinum(II) complexes [M(PP<sub>3</sub>)Cl]Cl [M = Pd (<b>1</b>), Pt (<b>2</b>)] (PP<sub>3</sub> = tris[2-(diphenylphosphino)ethyl]phosphine) were prepared by interaction of aqueous solutions of MCl<sub>4</sub><sup>2-</sup> salts with PP<sub>3</sub> in CHCl<sub>3</sub>. Complexes <b>1</b> and <b>2</b> undergo facile chloro substitution reactions with KCN in 1:1 and 1:2 ratios to afford complexes [M(PP<sub>3</sub>)(CN)]Cl [M = Pt (<b>3</b>)] and [M(PP<sub>3</sub>)(CN)](CN) [M = Pd (<b>4</b>), Pt (<b>5</b>)] possessing M−C bonds, both in solution and in the solid state. The reaction of <b>1</b> and <b>2</b> with SnCl<sub>2</sub> in CDCl<sub>3</sub> occurs with insertion of SnCl<sub>2</sub> into M−Cl bonds leading to the formation of [M(PP<sub>3</sub>)(SnCl<sub>3</sub>)](SnCl<sub>3</sub>) [M = Pd (<b>6</b>), M = Pt (<b>7</b>)]. The isolation as solids of complexes <b>6</b> and <b>7</b> by addition of SnCl<sub>2</sub> to the precursors requires the presence of PPh<sub>3</sub> which activates the cleavage of M−Cl bonds, favors the SnCl<sub>2</sub> insertion, and does not coordinate to M in any observable extent. Solutions of <b>6</b> in CDCl<sub>3</sub> undergo tin dichloride elimination in higher proportion than solutions of <b>7</b>. The reaction of complexes <b>1</b> and <b>2</b> with SnPh<sub>2</sub>Cl<sub>2</sub> leads to [M(PP<sub>3</sub>)Cl]<sub>2</sub>[SnPh<sub>2</sub>Cl<sub>4</sub>] [M = Pd (<b>8</b>)]. Complexes <b>2</b>, <b>5</b>, <b>7</b>, and <b>8</b> were shown by X-ray diffraction to contain distorted trigonal bipyramidal monocations [M(PP<sub>3</sub>)X]<sup>+</sup> [M = Pt, X = Cl<sup>-</sup> (<b>2</b>), X = CN<sup>-</sup> (<b>5</b>), X = SnCl<sub>3</sub><sup>-</sup> (<b>7</b>); M = Pd, X = Cl<sup>-</sup> (<b>8</b>)], the central P atom of PP<sub>3</sub> being trans to X in axial position and the terminal P donors in the equatorial plane of the bipyramids. The “preformed” catalyst <b>7</b> showed a relatively high aldehyde selectivity compared to most of the platinum catalysts. SnPh 2 Cl 4;SnPh 2 Cl 2;chloro substitution reactions;solution;bond;Pt;Pd;Complexe;KCN;terminal P donors;SnCl 2 insertion;SnCl 2;CN;tin dichloride elimination;PP 3;CDCl 3;complex 2002-07-27
    https://acs.figshare.com/articles/dataset/Preparation_and_Structural_Characterization_of_Ionic_Five-Coordinate_Palladium_II_and_Platinum_II_Complexes_of_the_Ligand_Tris_2-_diphenylphosphino_ethyl_phosphine_Insertion_of_SnCl_sub_2_sub_into_M_Cl_Bonds_M_Pd_Pt_and_Hydroformylation_Activity_of_the_Pt/3605457
10.1021/ic020006k.s001