title: Synthesis and microwave spectrum of (2-chloroethyl)phosphine (ClCH(2)CH(2)PH(2)).
abstract: The synthesis of a 2-halogenoethylphosphine, (2-chloroethyl)phosphine (ClCH(2)CH(2)PH(2)), is reported for the first time. This compound was prepared by a chemoselective reduction of diethylchloroethylphosphonate with dichloroalane using a vacuum line. (2-Chloroethyl)phosphine has been studied by microwave spectroscopy at room temperature, or at -20 degrees C, in the 22-80 GHz spectral interval. The experimental study has been augmented by quantum chemical calculations at the MP2/6-311++(3df,3pd) and B3LYP/6-311++(3df,3pd) levels of theory. The spectra of two rotameric forms, denoted I and II have been assigned. These conformers both have an antiperiplanar arrangement for the Cl-C-C-P chain of atoms, but with different orientation of the phosphine group. Conformer I was found to be 5.2(6) kJ/mol more stable than II by relative intensity measurements. The spectra of the first excited states of the C-C torsional vibration of both I and II were assigned. The torsional frequency was determined to be 63(20) cm(-1) for conformer I by relative intensity measurements, and it has a similar value in II. It was found that this normal vibration deviates from a near-harmonic behavior. The quantum chemical calculations produce rotational and centrifugal distortion constants that are in satisfactory agreement with observations, but fail to predict correctly low-frequency fundamental frequencies. The quantum chemical calculations indicate that three additional conformers characterized by a synclinal orientation for the Cl-C-C-P link of atoms and with different orientation of the phosphine group are high-energy forms of ClCH(2)CH(2)PH(2). Searches for these forms were unsuccessful.
authors.affiliation: Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, NO-0315 Oslo, Norway. harald.mollendal@kjemi.uio.no
authors.forename: Harald
authors.initials: H
authors.lastname: Møllendal
authors.forename: Alexey
authors.initials: A
authors.lastname: Konovalov
authors.forename: Jean-Claude
authors.initials: JC
authors.lastname: Guillemin