Structures of tetrasilylmethane derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the gas phase, and their dynamic structures in solution

TY - JOUR

T1 - Structures of tetrasilylmethane derivatives (XMe2Si)2C(SiMe3)2 (X = H, Cl, Br) in the gas phase, and their dynamic structures in solution

AU - Wann, Derek A.

AU - Robinson, Matthew S.

AU - Bätz, Karin

AU - Masters, Sarah L.

AU - Avent, Anthony G.

AU - Lickiss, Paul D.

N1 - © 2015 American Chemical Society. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details

PY - 2015/1/29

Y1 - 2015/1/29

N2 - The structures of the molecules (XMe2Si)2C(SiMe3)2, where X = H, Cl, Br, have been determined by gas electron diffraction (GED) using the SARACEN method of restraints, with all analogues existing in the gas phase as mixtures of C1- and C2-symmetric conformers. Variable temperature 1H and 29Si solution-phase NMR studies, as well as 13C NMR and 1H/29Si NMR shift correlation and 1H NMR saturation transfer experiments for the chlorine and bromine analogues, are reported. At low temperatures in solution there appear to be two C1 conformers and two C2 conformers, agreeing with the isolated-molecule calculations used to guide the electron diffraction refinements. For (HMe2Si)2C(SiMe3)2 the calculations indicated six conformers close in energy, and these were modeled in the GED refinement.

AB - The structures of the molecules (XMe2Si)2C(SiMe3)2, where X = H, Cl, Br, have been determined by gas electron diffraction (GED) using the SARACEN method of restraints, with all analogues existing in the gas phase as mixtures of C1- and C2-symmetric conformers. Variable temperature 1H and 29Si solution-phase NMR studies, as well as 13C NMR and 1H/29Si NMR shift correlation and 1H NMR saturation transfer experiments for the chlorine and bromine analogues, are reported. At low temperatures in solution there appear to be two C1 conformers and two C2 conformers, agreeing with the isolated-molecule calculations used to guide the electron diffraction refinements. For (HMe2Si)2C(SiMe3)2 the calculations indicated six conformers close in energy, and these were modeled in the GED refinement.

UR - http://www.scopus.com/inward/record.url?scp=84921854815&partnerID=8YFLogxK

U2 - 10.1021/jp511301s

DO - 10.1021/jp511301s

M3 - Article

AN - SCOPUS:84921854815

SN - 1089-5639

VL - 119

SP - 786

EP - 795

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 4

ER -