TY - JOUR

T1 - The molecular structure of difluoroisocyanato silane: A combined microwave spectral and theoretical study

AU - Guirgis, Gamil A.

AU - Wang, Zichao

AU - Lirjoni, Jonel

AU - Palmer, Michael H.

AU - Obenchain, Daniel A.

AU - Peebles, Rebecca A.

AU - Peebles, Sean A.

PY - 2010/11/1

Y1 - 2010/11/1

N2 - The microwave (MW) spectrum of HF2SiNCO (1) has been obtained and analyzed in the I-r representation for C-s symmetry. The rotational constants (RC) are: A 7111.28104(179), B 1565.77581(49) and C 1347.52275(77) MHz; the centrifugal distortion constants are: Delta(J) 2.661(11), Delta(JK) 455.44(25), delta(J) 0.4237(51), phi(K) -54.96(29) kHz: the N-14 nuclear quadrupole coupling constants are: chi(aa) +1.8833(27) and (chi(bb) - chi(cc)) -0.0214(58) MHz. The low value for (chi(bb) - chi(cc)) implies a nearly linear SiNC structure, while the experimental A value is only consistent with cis-HSiNC and trans-SiNCO orientations.The MW analysis was assisted by calculations of the equilibrium structure. Whilst small bases give a linear SiNCO skeleton, a 6-311G(++) (3df,3pd) basis set calculation shows that the molecule is quasi-linear for all four methodologies: OFT, MP2, MP4 or CCSD(T). However, all these methods find the lowest energy conformer has trans-HSiNC and trans-SiNCO dihedral angles, although the energy difference is very small. The internal rotation barrier for the HF2Si group is less than 1 cm(-1), with the lower energy conformer having a trans-HSiNC moiety.The calculated SiNC angles for the cis-HSiNC conformer are: 171.2 (B3LYP), 167.7 (MP2), 154.9 (MP4) and 154.6 degrees (CCSD(T)), with differences up to 9 degrees (MP2) in the trans-series. The potential energy (PE) surface for SiNC bending (x) is unsymmetrical, but the differences from a symmetric form are very small. A B3LYP study leads to a polynomial fit of the SiNC angle (x, radians) with the energy (E, cm(-1)), where E = 1993(536)x(2) - 422(134)x(4) + 27(10)x(6) - 0.5(2)x(8); the alternating signs indicate a double minimum potential. We have re-determined the PE surfaces for silyl group rotation for several other isocyanates using similar methods. (C) 2010 Elsevier B.V. All rights reserved.

AB - The microwave (MW) spectrum of HF2SiNCO (1) has been obtained and analyzed in the I-r representation for C-s symmetry. The rotational constants (RC) are: A 7111.28104(179), B 1565.77581(49) and C 1347.52275(77) MHz; the centrifugal distortion constants are: Delta(J) 2.661(11), Delta(JK) 455.44(25), delta(J) 0.4237(51), phi(K) -54.96(29) kHz: the N-14 nuclear quadrupole coupling constants are: chi(aa) +1.8833(27) and (chi(bb) - chi(cc)) -0.0214(58) MHz. The low value for (chi(bb) - chi(cc)) implies a nearly linear SiNC structure, while the experimental A value is only consistent with cis-HSiNC and trans-SiNCO orientations.The MW analysis was assisted by calculations of the equilibrium structure. Whilst small bases give a linear SiNCO skeleton, a 6-311G(++) (3df,3pd) basis set calculation shows that the molecule is quasi-linear for all four methodologies: OFT, MP2, MP4 or CCSD(T). However, all these methods find the lowest energy conformer has trans-HSiNC and trans-SiNCO dihedral angles, although the energy difference is very small. The internal rotation barrier for the HF2Si group is less than 1 cm(-1), with the lower energy conformer having a trans-HSiNC moiety.The calculated SiNC angles for the cis-HSiNC conformer are: 171.2 (B3LYP), 167.7 (MP2), 154.9 (MP4) and 154.6 degrees (CCSD(T)), with differences up to 9 degrees (MP2) in the trans-series. The potential energy (PE) surface for SiNC bending (x) is unsymmetrical, but the differences from a symmetric form are very small. A B3LYP study leads to a polynomial fit of the SiNC angle (x, radians) with the energy (E, cm(-1)), where E = 1993(536)x(2) - 422(134)x(4) + 27(10)x(6) - 0.5(2)x(8); the alternating signs indicate a double minimum potential. We have re-determined the PE surfaces for silyl group rotation for several other isocyanates using similar methods. (C) 2010 Elsevier B.V. All rights reserved.

U2 - 10.1016/j.molstruc.2010.07.044

DO - 10.1016/j.molstruc.2010.07.044

M3 - Article

VL - 983

SP - 5

EP - 11

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

IS - 1-3

ER -