Molecular Structure of Methyldifluoroisocyanato Silane: A Combined Microwave Spectral and Theoretical Study

Abstract

The structure of methyldifluoroisocyanato silane, MeF2SiNCO (2), has been studied by molecular rotational spectroscopy. The rotational spectrum has a complicated structure from (14)N nuclear quadrupole coupling and internal rotation of the methyl group. Cavity Fourier-transform microwave spectroscopy measurements were important for providing high spectral resolution to analyze the quadrupole and internal rotation fine structure. Broadband chirped-pulse Fourier-transform microwave spectroscopy was used to achieve high measurement sensitivity making it possible to observe the lower abundance C, N, O, and Si isotopologues in natural abundance for structure determination. Analysis of the microwave spectrum of the most abundant isotopomer of MeF2SiNCO (2) yields the rotational constants: A = 3827.347(7), B = 1264.5067(14), and C = 1240.6182(11) MHz. The spectrum has been analyzed in the I(r) representation for Cs symmetry, with inclusion of the 3-fold rotor (V3 = 446(50) cm(-1)). A partial substitution structure was obtained for the C, Si, N, and O atoms. The analysis was assisted by calculations of the equilibrium structure, using a 6-311++G (3df, 3pd) basis set, with calculations at each of the B3LYP, MP2, and CCSD(T) levels. The calculated and experimental rotational constants are only consistent with a trans-orientation at each of the HCSiN, CSiNC, and SiNCO centers; there is relatively close agreement between the experimental and the theoretical structures, especially at the CCSD(T) level. In addition, the observed low value for the (14)N quadrupole coupling term (χbb - χcc) implies a wide SiNC angle, which is consistent with the calculated values: 165.3° (B3LYP), 157.6° (MP2), and 157.4° (CCSD(T)). The skeletal bending potential is discussed.