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Through‐Space J (P,P) and J (P,F) Spin–Spin Coupling in C 1 ‐Symmetric Biaryl Diphosphanes
Author(s) -
Bonnafoux Laurence,
Ernst Ludger,
Leroux Frédéric R.,
Colobert Françoise
Publication year - 2011
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/ejic.201100428
Subject(s) - chemistry , heteronuclear molecule , coupling constant , lone pair , crystallography , spin (aerodynamics) , biphenyl , heteronuclear single quantum coherence spectroscopy , spectral line , two dimensional nuclear magnetic resonance spectroscopy , nuclear magnetic resonance spectroscopy , molecular physics , molecule , stereochemistry , quantum mechanics , physics , organic chemistry , thermodynamics
The first simultaneous 31 P, 31 P and 31 P, 19 F solution‐phase through‐space nuclear spin–spin coupling in biphenyl derivatives is reported. The magnitudes of the coupling constants are in the range 5.3–28.7 and 2.3–5.1 Hz, respectively. Their observation became possible through access to a recently developed class of C 1 ‐symmetric biphenyl diphosphanes. We used this to prepare a series of model compounds for the study of the through‐space couplings. Various 1D and 2D techniques [COSY, NOESY, heteronuclear single quantum coherence (HSQC), HMBC, HSCQ‐TOCSY, selective 1 H{ 31 P}‐decoupling and iterative bandshape analysis] were applied to assign the 1 H, 13 C, 19 F and 31 P NMR spectra as completely as possible. X‐ray structure determinations confirmed the structural assignments and afforded P ··· P distances and torsion angles in the solid state. No simple correlation was found between the experimental J ( 31 P, 31 P) values in solution and the relevant geometric parameters (P ··· P distance and torsional angle between the phosphorus lone pairs) in the solid state.