Indexed on: 19 Dec '14Published on: 19 Dec '14Published in: Chemistry - A European Journal
Hydrometallation of iPr2 N-Ge(CMe3 )(C≡C-CMe3 )2 with H-M(CMe3 )2 (M=Al, Ga) affords alkenyl-alkynylgermanes in which the Lewis-acidic metal atoms are not coordinated by the amino N atoms but by the α-C atoms of the ethynyl groups. These interactions result in a lengthening of the Ge-C bonds by approximately 10 pm and a comparably strong deviation of the Ge-CC angle from linearity (154.3(1)°). This unusual behaviour may be caused by steric shielding of the N atoms. Coordination of the metal atoms by the amino groups is observed upon hydrometallation of Et2 N-Ge(C6 H5 )(C≡C-CMe3 )2 , bearing a smaller NR2 group. Strong M-N interactions lead to a lengthening of the Ge-N bonds by 10 to 15 pm and a strong deviation of the M atoms from the MC3 plane by 52 and 47 pm, for Al and Ga, respectively. Dual hydrometallation is achieved only with HAl(CMe3 )2 . In the product, there is a strong Al-N bond with converging Al-N and Ge-N distances (208 vs. 200 pm) and an interaction of the second Al atom to the phenyl group. Addition of chloride anions terminates the latter interaction while the activated Ge-N bond undergoes an unprecedented elimination of EtN=C(H)Me at room temperature, leading to a germane with a Ge-H bond. State-of-the-art DFT calculations reveal that the unique mechanism comprises the transfer of the amino group from Ge to Al to yield an intermediate germyl cation as a strong Lewis acid, which induces β-hydride elimination, with chloride binding being crucial for providing the thermodynamic driving force.