An enormous vibrational motion: the gas-phase structure of dimethyl-bis(methoxyethynyl) germanium.
The structure of dimethyl-bis(methoxyethynyl) germanium has been determined in the gas phase by electron diffraction utilising flexible restraints from quantum chemical calculations. Theoretical methods (B3LYP/6-311+G* and MP2/6-311+G*) predict a low barrier to rotation of the methoxy groups in the molecule in addition to low-frequency vibrations of the long ethynyl chains. In the equilibrium structure the Ge-C[triple bond]C angles of the two methoxyethynyl fragments in the molecule are computed to deviate by up to 4 degrees from the linear arrangement. As a consequence of low-frequency large-amplitude vibrational motion the experimental structure of these fragments without applying vibrational corrections deviates considerably from linearity, while the structure corrected for vibrational effects using the harmonic approximation and taking into account a non-linear transformation between internal and Cartesian coordinates (r(h1)) shows closer agreement with theory. The main experimental structural parameters of dimethyl-bis(methoxyethynyl) germanium (r(h1)) are: r(Ge-C)(mean), 192.5(1) pm; DeltaGeC =r(Ge-C(methyl))-r(Ge-C(ethynyl)), 4.5(5) pm, r(C[triple bond]C)(mean), 122.8(2) pm; r(C-O)(mean), 138.9(3) pm; DeltaCO =r(C(methyl)-O)-r(C(ethynyl)-O), 14.5(2) pm, r(C-H)(mean), 109.1(4) pm; [angle](X-C-H)(mean)(X = Ge,O), 109(1) degree; [angle]C(ethynyl)-Ge-C(ethynyl), 108.1(4) degree; [angle]C(methyl)-Ge-C(methyl), 113.4(5) degree; [angle]Ge-C[triple bond]C, 163(1) degree; [angle]C[triple bond]C-O, 176(2) degree; [angle]C-O-C, 115.2(6) degree; methoxy group torsion, tau, 36(9) degree from the position in which the C-O bond eclipses the further Ge-C(ethynyl) bond.
Borisenko
Konstantin B
KB
School of Chemistry, University of Edinburgh, West Mains Road, Edinburgh EH9 3JJ, Scotland, UK.
Yezhov
Roman N
RN
Gruener
Sergej V
SV
Robertson
Heather E
HE
Rankin
David W H
DW