title: A microwave spectroscopic and quantum chemical study of propa-1,2-dienyl selenocyanate (H(2)==C==CHSeC[triple bond]N) and cyclopropyl selenocyanate (C(3)H(5)SeC[triple bond]N).
abstract: The microwave spectra of propa-1,2-dienyl selenocyanate, H(2)C==C==CHSeC[triple bond]N, and cyclopropyl selenocyanate, C(3)H(5)SeC[triple bond]N, are reported. The spectra of the ground and two vibrationally excited states of the (80)Se isotopologue and the spectrum of the ground state of the (78)Se isotopologue were assigned for one rotameric form of H(2)C==C[double bond, length as m-dash]CHSeC[triple bond]N. This conformer is characterized by a C-C-Se-C dihedral angle of 129(5) degrees from synperiplanar (0 degrees ) and is shown to be the global minimum of H(2)C[double bond, length as m-dash]C[double bond, length as m-dash]CHSeC[triple bond]N. The spectra of the ground and of three vibrationally excited states of the (80)Se isotopologue, as well as of the ground state of the (78)Se isotopologue of one rotamer of C(3)H(5)SeC[triple bond]N were assigned. This conformer has a H-C-Se-C dihedral angle of 80(4) degrees from synperiplanar and is at least 3 kJ mol(-1) more stable than any other form of the molecule. The microwave study has been augmented by quantum chemical calculations at the B3LYP/6-311+ +G(3df,3pd) and MP2/6-311+ +G(3df,3pd) levels of theory.
authors.affiliation: Department of Chemistry, University of Oslo, P. O. Box 1033 Blindern, NO-0315, Oslo, Norway.
authors.forename: Rajmund
authors.initials: R
authors.lastname: Mokso
authors.forename: Harald
authors.initials: H
authors.lastname: Møllendal
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Guillemin
mesh_terms: D003485:Cyanates / Q000737:chemistry*; D003521:Cyclopropanes / Q000737:chemistry*; D008872:Microwaves; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D018036:Selenium Compounds / Q000737:chemistry*; D013057:Spectrum Analysis
chemical_list: D003485:Cyanates; D003521:Cyclopropanes; D018036:Selenium Compounds; C532860:cyclopropyl selenocyanate; C532859:propa-1,2-dienyl selenocyanate; C053721:selenocyanic acid