The Molecular Structures and Conformations of Bis(dichlorosilyl)amine and 
Bis(dichlorosilyl)methylamine in the Gas Phase: Determination by Electron 
Diffraction and by ab Initio Calculations

Fleischer, Holger; Hnyk, Drahomír; Rankin, David W. H.; Robertson, Heather E.; Bühl, Michael; Thiel, Walter

doi:10.1002/cber.19951280812

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The Molecular Structures and Conformations of Bis(dichlorosilyl)amine and Bis(dichlorosilyl)methylamine in the Gas Phase: Determination by Electron Diffraction and by ab Initio Calculations

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Fleischer, H., Hnyk, D., Rankin, D. W. H., Robertson, H. E., Bühl, M., & Thiel, W. (1995). The Molecular Structures and Conformations of Bis(dichlorosilyl)amine and Bis(dichlorosilyl)methylamine in the Gas Phase: Determination by Electron Diffraction and by ab Initio Calculations. Chemische Berichte, 128(8), 807-815. doi:10.1002/cber.19951280812.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0027-F3DF-C

Abstract

The gas-phase molecular structures of bis(dichlorosilyl)-amine, (HSiCl₂)₂NH, and bis(dichlorosilyl)methylamine, (SiHCl₂)₂NMe, have been investigated by electron diffraction and ab initio calculations on a MP2/6–31G* level. Because the latter suggest the presence of a mixture of two conformers for each molecule, attempts were made to fit the electron diffraction data in each case by two different models, one assuming the presence of only one conformation, and another allowing for two different conformers. The principal parameters (r_a) from electron diffraction for (HSiCl₂)₂NH are (the appropriate ab initio calculated values are given in brackets []): r(Si-N) 171.9(2) [172.7], r(Si-Cl) 204.1(1)[204.5] pm; Si-N-Si 126.5(8) [127.4] N-Si-Cl 107.3(5) [110.8] and Cl-Si-Cl 106.5(3) [107.5]°. For (SiHCl₂)₂NMe: r(Si-N) 171.1(3) [171.5], r(Si-Cl) 204.0(9) [205.2], r(N-C) 149.7(10) [148.3] pm; Si-N-Si 124.9(13) [123.4], N-Si-Cl 109.7(5) [110.7] and Cl-Si-Cl 107.1(3) [107.2]° [110.8] and Cl-Si-Cl 106.5(3) [107.5]°. For (SiHCl2)2NMe: r(Si-N) 171.1(3) [171.5], r(Si-Cl) 204.0(9) [205.2], r(N-C) 149.7(10) [148.3] pm; Si-N-Si 124.9(13) [123.4], N-Si-Cl 109.7(5) [110.7] and Cl-Si-Cl 107.1(3) [107.2]°. For (HSiCl₂)₂NH three different conformers were found to fit the experimental data with the single-conformation model. In two of the conformers, the dichlorosilyl groups are twisted by Θ₁ = 146.0(10)/Θ₂ = 155.2(20)° and Θ₁= 101.1(49)/Θ₂ = 196.8(12)°; respectively counterclockwise from the positions in which the Si-H bonds eclipse the N-H bond. Both of these lead to nearly ideally staggered conformations of the two SiHCl₂ groups when viewed along the Si–Si axis. In contrast, the third conformation is nearly eclipsed, with torsion angles Θ₁ = 131.4(15)/Θ₂ = 80.4(26)°. Planarity of the Si₂NH group was assumed as suggested by ab initio calculation. For (HSiCl₂)₂NMe the experimental data could be suitably fitted by two conformers, in which the dichlorosilyl groups are twisted by Θ₁= 161.8(13)/Θ = 63.1(23)° and Θ₁ = 156.1(9)/ Θ₂ = 177.1(15)° from the positions in which the Si-H bonls eclipse the N-C bond. The first of these structures has an eclipsed Si(NSi)Cl conformation and an Si…Cl nonbonded distance close to distance clse to the sum of the appropriate van der waals radii. MP2/6–31G* calculations support the GED bond lengths and bond angles of both molecules, but indicate different conformations for the most stable equilibrium geometries: the computed twists are Θ₁ = 180/Θ₂ = 180° and Θ₁ = 177.0/ Θ₂ = 183.0° for (HSiCl₂)₂NH and (HSiCl₂)₂NMe, respectively. Rotation about the Si—N bonds is a very facile process, cf. the computed [MP2/6–31G*//MP2/6–31G* + ZPE(SCF/6–31G*)] rotational barrier of 2.9 kJ. mol^-1 for (HSiCl₂)₂NH.