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Solid‐state and Solution‐state NMR Studies of the Chlorophosphane (2,6‐(CF 3 ) 2 C 6 H 3 )(2,4‐(CF 3 ) 2 C 6 H 3 )PCl, (Ar′Ar′′PCl), and its Crystal Structure at 150 K
Author(s) -
Batsanov Andrei S.,
Cornet Stephanie M.,
Crowe Lindsey A.,
Dillon Keith B.,
Harris Robin K.,
Hazendonk Paul,
Roden Mark D.
Publication year - 2001
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/1099-0682(200107)2001:7<1729::aid-ejic1729>3.0.co;2-o
Subject(s) - chemistry , state (computer science) , solid state , crystallography , computational chemistry , algorithm , computer science
The title compound has been synthesised, and characterised by multinuclear magnetic resonance spectroscopy, both in solution and in the solid state. The bandshapes of variable‐temperature solution‐state 19 F NMR spectra have been iteratively fitted to obtain information on the kinetics of rotation about the P−C bond for one of the aryl groups, and values for the enthalpy and entropy of activation of the process have been derived. Magic‐angle spinning NMR techniques have been extensively applied to the solid, using 19 F, 31 P and 13 C nuclei. Triple‐channel methods and different magnetic field strengths have been employed to yield a range of complementary information. Heteronuclear interactions and intramolecular motions have been investigated. Bandshapes arising from (P, Cl) residual dipolar coupling have been analysed. Satisfactory agreement is found between experimental spectra and those simulated with estimated values of the parameters involved, and it is confirmed that the electric field gradient at chlorine is co‐axial with the P−Cl bond. The sign of the isotropic (P−Cl) indirect coupling constant is obtained for the first time and is shown to be negative. The crystal structure of the compound at 150 K confirms the presence of two different aromatic residues, as deduced from the spectroscopic studies.