Document Detail


Microwave spectrum, and conformational composition of (chloromethyl)phosphine (ClCH2PH2).
MedLine Citation:
PMID:  20836524     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
(Chloromethyl)phosphine, (ClCH(2)PH(2)) has been studied by microwave spectroscopy at -30 °C in the 22-80 GHz spectral interval. The experimental study has been augmented by quantum chemical calculations at the MP2/aug-cc-pVQZ and B3LYP/aug-cc-pVTZ levels of theory. The spectra of the ground as well as of several vibrationally excited states of the (35)ClCH(2)PH(2) and (37)ClCH(2)PH(2) isotopologues of two rotameric forms, denoted I and II, have been assigned. These conformers have different orientations of the phosphino group. I has a symmetry plane, consisting of the Cl-C-P link of atoms, whereas the phosphino group is rotated out of this symmetry plane in II. Conformer I was found to be 4.3(5) kJ/mol more stable than II by relative intensity measurements. The rotational and quartic centrifugal distortion constants calculated using the MP2/aug-cc-pVQZ procedure are in very good agreement with their experimental counterparts. Less good agreement is found in the B3LYP/aug-cc-pVTZ calculations. Both computational procedures predict energy differences between I and II that are close to the experimental energy difference. It is suggested that I is the preferred form of this molecule because it is stabilized by weak intramolecular hydrogen bonding between the chlorine atom and the hydrogen atoms of the phosphino group. Repulsion between the lone electron pair of the phosphorus atom and the chlorine atom also stabilizes I relative to II.
Authors:
Harald Møllendal; Alexey Konovalov; Jean-Claude Guillemin
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  114     ISSN:  1520-5215     ISO Abbreviation:  J Phys Chem A     Publication Date:  2010 Oct 
Date Detail:
Created Date:  2010-09-30     Completed Date:  2011-01-21     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  10612-8     Citation Subset:  IM    
Affiliation:
Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, NO-0315 Oslo, Norway. harald.mollendal@kjemi.uio.no
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MeSH Terms
Descriptor/Qualifier:
Hydrocarbons, Chlorinated / chemistry*
Microwaves*
Molecular Conformation
Molecular Dynamics Simulation
Phosphines / chemistry*
Quantum Theory
Chemical
Reg. No./Substance:
0/Hydrocarbons, Chlorinated; 0/Phosphines; 0/chloromethyl phosphine

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