Gas-phase structures of sterically crowded disilanes studied by electron diffraction and quantum chemical methods : 1,1,2,2-tetrakis(trimethylsilyl) disilane and 1,1,2,2-tetrakis(trimethylsilyl)dimethyldisilane

The gas-phase structures of the disilanes 1,1,2,2-tetrakis(trimethylsilyl) disilane [(Me3Si)2HSiSiH(SiMe3)2] (1) and 1,1,2,2-tetrakis(trimethylsilyl)dimethyldisilane [(Me 3Si)2MeSiSiMe(SiMe3)2] (2) have been determined by density functional theoretical calculations and by gas electron diffraction (GED) employing the SARACEN method. For each of 1 and 2 DFT calculations revealed four C2-symmetric conformers occupying minima on the respective potential-energy surfaces; three conformers were estimated to be present in sufficient quantities to be taken into account when fitting the GED data. For (Me3Si)2RSiSiR(SiMe3)2 [R = H (1), CH3 (2)] the lowest energy conformers were found by GED to have RSiSiR dihedral angles of 87.7(17)° for 1 and -47.0(6)° for 2. For each of 1 and 2 the presence of bulky and flexible trimethylsilyl groups dictates many aspects of the geometric structures in the gas phase, with the molecules often adopting structures that reduce steric strain

Crystallographic characterization of a palladium(II) metallamacrocycle supported by an amino-functionalized ferrocene and its use as an efficient Suzuki-coupling catalyst

10.1021/om049911yOrganometallics23153603-3609ORGN