10.1021/om050214v.s003
Isabelle Saur
Isabelle
Saur
Sonia Garcia Alonso
Sonia
Garcia Alonso
Heinz Gornitzka
Heinz
Gornitzka
Virginie Lemierre
Virginie
Lemierre
Anna Chrostowska
Anna
Chrostowska
Jacques Barrau
Jacques
Barrau
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>
American Chemical Society
2005
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
2005-06-06 00:00:00
Dataset
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.