3767-37-1Relevant academic research and scientific papers
Electron distribution in a stable carbene
Arduengo III, Anthony J.,Dias, H. V. Rasika,Dixon, David A.,Harlow, Richard L.,Klooster,Koetzle
, p. 6812 - 6822 (1994)
The synthesis and characterization of the stable carbene perdeuterio-1,3,4,5-tetramethylimidazol-2-ylidene (2) are reported. The neutron and X-ray diffraction data from single crystals of this perdeuterocarbene are used to determine the electron distribution in the molecule. Neutron diffraction data were collected at 80 and 173K on 2. The experimentally determined electron density is very closely matched by density functional calculations which show that 2 is a true carbene with negligible ylidic character.
Infrared and Raman spectra, conformational stability, ab initio calculations, and vibrational assignments for methylaminothiophosphoryl difluoride
Van Der Veken,Sanders,Xiao,Durig
, p. 57 - 86 (2007/10/03)
Infrared spectra (4000-50 cm-1) of the vapor, amorphous and crystalline solids and Raman spectra (3600-10 cm-1) of the liquid with qualitative depolarization data as well as the amorphous and crystalline solids of methylaminothiophosphoryl difluoride, CH3N(H)P(=S)F2, and three deuterated species, CD3N(H)P(=S)F2, CH3N(D)P(=S)F2, and CD3N(D)P(=S)F2, have been recorded. The spectra indicate that in the vapor, liquid and amorphous solid a small amount of a second conformer is present, whereas only one conformer remains in the low temperature crystalline phase. The near-infrared spectra of the vapor confirms the existence of two conformers in the gas phase. Asymmetric top contour simulation of the vapor shows that the trans conformer is the predominant vapor phase conformer. From a temperature study of the Raman spectrum of the liquid the enthalpy difference between the trans and near-cis conformers was determined to be 368 ± 15 cm-1 (4.4l ± 0.2 kJ/mol), with the trans conformer being thermodynamically preferred. Ab Initio calculations with structure optimization using the 6-31G(d) and 6-311+G(d,p) basis sets at the restricted Hartree-Fock (RHF) and/or with full electron correlation by the perturbation method to second order (MP2) support the occurrence of near-trans (～5° from trans) and near-cis (～20° from cis) conformers. From the RHF/6-31G(d) calculation the near-trans conformer is predicted to be the more stable form by 451 cm-1 .(5.35 kJ/mol) and from the MP2/6-311+G(d,p) calculation by 387 cm-1 (4.63 kJ/mol). All of the normal modes of the near-trans rotamer have been assigned based on infrared band contours, depolarization values and group frequencies and the assignment is supported by the normal coordinate calculation utilizing harmonic force constants from the MP2/6-31G(d) ab initio calculations.
