In Search of Cationic Germanium(II)−Transition Metal Complexes L<sup>2</sup>Ge<sup>+</sup>W(CO)<sub>5</sub> and L<sup>2</sup>Ge<sup>+</sup>W(CO)<sub>4</sub>Ge<sup>+</sup>L<sup>2</sup> Isabelle Saur Sonia Garcia Alonso Heinz Gornitzka Virginie Lemierre Anna Chrostowska Jacques Barrau 10.1021/om050214v.s003 https://acs.figshare.com/articles/dataset/In_Search_of_Cationic_Germanium_II_Transition_Metal_Complexes_L_sup_2_sup_Ge_sup_sup_W_CO_sub_5_sub_and_L_sup_2_sup_Ge_sup_sup_W_CO_sub_4_sub_Ge_sup_sup_L_sup_2_sup_/3283369 New germanium(II)−tungsten complexes [L<sup>2</sup>(X)Ge]<i><sub>n</sub></i>W(CO)<sub>6</sub><sub>-</sub><i><sub>n</sub></i> (L<sup>2</sup> = NPhC(Me)CHC(Me)NPh, <i>n</i> = 1, X = OTf (<b>2</b>); <i>n</i> = 2, X = Cl (<b>13</b>)) have been synthesized and characterized by X-ray crystallography. In compound <b>2</b> the triflate was found to be very weakly coordinating to the germanium in the solid state, and this result is confirmed by DFT calculations. All the spectroscopic data are consistent with the L<sup>2</sup>(X)Ge ligands being good σ-donors and poor π-acceptors in these complexes, similar to the phosphine ligands in homologous R<sub>3</sub>P complexes. Starting from the chlorogermanium(II)−tungsten complexes (L<sup>2</sup>(Cl)Ge)<i><sub>n</sub></i>W(CO)<sub>6</sub><sub>-</sub><i><sub>n</sub></i> (<i>n</i> = 1 (<b>1</b>), <i>n</i> = 2 (<b>13</b>)), metathesis reactions with halide or weakly coordinating anions A<sup>-</sup> (A<sup>-</sup> = TfO<sup>-</sup>, BPh<sub>4</sub><sup>-</sup>, PF<sub>6</sub><sup>-</sup>) have been investigated as a general approach to obtain the cationic germanium species [L<sup>2</sup>Ge<sup>+</sup>]<i><sub>n</sub></i>W(CO)<sub>6</sub><sub>-</sub><i><sub>n</sub></i>. In the case of A<sup>-</sup> = TfO<sup>-</sup>, spontaneous dissociation of the anion leading to an equilibrium between a neutral and a cationic tetracoordinated germanium species is observed in coordinating solvents. Treatment of L<sup>2</sup>(X)Ge with MX<sub>3</sub> (M = Ga, X = Cl; M = In, X = I) afforded the neutral complexes L<sup>2</sup>MX<sub>2</sub> (M = Ga (<b>7</b>) and In (<b>8</b>)) by ligand transfer reactions. The crystal structure of <b>8</b> was determined by X-ray structure analysis. 2005-06-06 00:00:00 TfO anion Ga L 2 Ge L 2 ligand transfer reactions PF DFT Cl cationic germanium species complexes L 2 MX 2 cationic tetracoordinated germanium species R 3 P complexes