Structures of tetrasilylmethane derivatives C(SiXMe2)4 (X = H, F, Cl, Br) in the gas phase and their dynamic structures in solution.

TY - JOUR

T1 - Structures of tetrasilylmethane derivatives C(SiXMe2)4 (X = H, F, Cl, Br) in the gas phase and their dynamic structures in solution.

AU - Wann, Derek A.

AU - Young, Stuart

AU - Bätz, Karin

AU - Masters, Sarah L.

AU - Avent, Anthony G.

AU - Rankin, David W. H.

AU - Lickiss, Paul D.

N1 - M1 - Copyright (C) 2015 American Chemical Society (ACS). All Rights Reserved. This is an author-produced version of a paper accepted for publication. Uploaded with permission of the publisher/copyright holder. Further copying may not be permitted; contact the publisher for details

PY - 2014/12/19

Y1 - 2014/12/19

N2 - The structures of the molecules C(SiXMe2)4 (X = H, F, Cl, Br) have been determined by gas electron diffraction (GED). Ab initio calculations revealed nine potential minima for each species, with significant ranges of energies. For the H, F, Cl, and Br derivatives nine, seven, two, and two conformers were modelled, respectively, as they were quantum-chemically predicted to be present in measurable quantities. Variable-temperature 1H and 29Si solution-phase NMR studies and, where applicable, 13C NMR, 1H/29Si NMR shift-correlation, and 1H NMR saturation-transfer experiments are reported for C(SiXMe2)4 (X = H, Cl, Br, and also I). At low temperature in solution two conformers (one C1-symmetric and one C2-symmetric) are observed for each of C(SiXMe2)4 (X = Cl, Br, I), in agreement with the isolated molecule ab initiocalculations carried out as part of this work for X = Cl, Br. C(SiHMe2)4 is present as a single C1-symmetric conformer in solution at the temperatures at which the NMR experiments were performed.

AB - The structures of the molecules C(SiXMe2)4 (X = H, F, Cl, Br) have been determined by gas electron diffraction (GED). Ab initio calculations revealed nine potential minima for each species, with significant ranges of energies. For the H, F, Cl, and Br derivatives nine, seven, two, and two conformers were modelled, respectively, as they were quantum-chemically predicted to be present in measurable quantities. Variable-temperature 1H and 29Si solution-phase NMR studies and, where applicable, 13C NMR, 1H/29Si NMR shift-correlation, and 1H NMR saturation-transfer experiments are reported for C(SiXMe2)4 (X = H, Cl, Br, and also I). At low temperature in solution two conformers (one C1-symmetric and one C2-symmetric) are observed for each of C(SiXMe2)4 (X = Cl, Br, I), in agreement with the isolated molecule ab initiocalculations carried out as part of this work for X = Cl, Br. C(SiHMe2)4 is present as a single C1-symmetric conformer in solution at the temperatures at which the NMR experiments were performed.

KW - structure tetrasilylmethane deriv GED multinuclear NMR

U2 - 10.5560/ZNB.2014-4147

DO - 10.5560/ZNB.2014-4147

M3 - Article

SN - 0932-0776

VL - 69b

SP - 1321

EP - 1332

JO - Zeitschrift für Naturforschung. Section B: A Journal of Chemical Sciences

JF - Zeitschrift für Naturforschung. Section B: A Journal of Chemical Sciences

IS - 11/12

ER -