Spectroscopic and Quantum Chemical Study of the Novel Compound Cyclopropylmethylselenol George C. Cole, † Harald Møllendal,* ,† and Jean-Claude Guillemin ‡ Department of Chemistry, UniVersity of Oslo, Post Office Box 1033, Blindern, NO-0315 Oslo, Norway, and Laboratoire de Synthe ` se et ActiVation de Biomole ´ cules, Unite ´ Mixte de Recherche 6052 du Centre National de la Recherche Scientifique, Institut de Chimie de Rennes, Ecole Nationale Supe ´ rieure de Chimie de Rennes, F-35700 Rennes, France ReceiVed: October 18, 2005; In Final Form: December 14, 2005 An investigation into the properties of the novel compound cyclopropylmethylselenol has been undertaken by use of Stark-modulation microwave spectroscopy and high-level quantum chemical calculations. Ground- state spectra belonging to six isotopomers of a single conformer of the molecule were recorded and assigned. This conformer, predicted to be the lowest in energy by a series of quantum chemical calculations, possesses a synclinal arrangement of the H-C-C-Se atoms. In addition to the assignment of these ground-state spectra, transitions attributable to vibrationally excited states of the 78 Se- and 80 Se-containing isotopomers were identified. A tentative assignment of these excited-state spectra to specific vibrational modes has been made with the assistance of a density functional theory calculation at the B3LYP/6-311++G(3df,2pd) level of theory. Close agreement was found between experimental ground-state rotational constants and ab initio equilibrium values calculated at the MP2/aug-cc-pVTZ level of theory. Good agreement was also noted between certain r s principal axis coordinates of atoms in the molecule and the corresponding ab initio r e values. Limited evidence in favor of the formation of a weak intramolecular hydrogen bond between the H atom of the selenol group and electron density associated with the cyclopropyl ring is discussed. Introduction The ability of selenols to form intramolecular hydrogen bonds in the gas phase was first demonstrated in the case of 3-buteneselenol. 1 The lowest-energy conformer of this molecule is stabilized by an internal hydrogen bond between the H atom of the selenol group and the π electrons of the double bond. Few selenols have to date been studied by microwave (MW) spectroscopy, and no other example of a selenol forming an intramolecular hydrogen bond has been found. The fact that so few selenols have been studied is likely to be in part a consequence of their toxicity, instability toward air, and powerfully obnoxious odors. The subject of the current investigation, namely, cyclopro- pylmethylselenol, has been chosen in order to allow a direct comparison with the analogous alcohol (C 3 H 5 CHOH) 2-4 and thiol (C 3 H 5 CHSH) 5 molecules to be made. Both of these molecules have been shown to possess intramolecular hydrogen bonds, formed between the -XH (X ) O, S) group and electron density along the edge of the cyclopropyl ring. It is therefore of interest to determine whether cyclopropylmethylselenol can be stabilized by a similar interaction. Figure 1 shows the five possible conformers of cyclopropy- lmethylselenol. It can be seen that conformers II, III, and V are capable of forming an intramolecular H bond by means of a close approach between a Se-H group and the center of a C-C bond in the cyclopropyl group. Such an interaction is not possible for conformers I and IV. Experimental Section Microwave Experiment. The microwave spectrum of cy- clopropylmethylselenol was recorded in the 22-62 GHz * Corresponding author: e-mail harald.mollendal@kjemi.uio.no; tel. +47 2285 5674; fax +47 2285 5441. † University of Oslo. ‡ Ecole Nationale Supe ´rieure de Chimie de Rennes. Figure 1. Structures of the five conformers of cyclopropylmethylse- lenol, as obtained from geometry optimizations performed at the MP2/ aug-cc-pVTZ level of theory with the Gaussian 03 electronic structure package. 2134 J. Phys. Chem. A 2006, 110, 2134-2138 10.1021/jp055955o CCC: $33.50 © 2006 American Chemical Society Published on Web 01/21/2006