Premium
Probing the proton‐transfer coordinate of complexes with FH…P hydrogen bonds using one‐ and two‐bond spin–spin coupling constants
Author(s) -
Del Bene Janet E.,
Elguero José
Publication year - 2007
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.2025
Subject(s) - chemistry , coupling constant , trimethylphosphine , hydrogen bond , phosphine , proton , spin (aerodynamics) , crystallography , coupling (piping) , hydrogen , computational chemistry , molecule , thermodynamics , crystal structure , quantum mechanics , physics , organic chemistry , catalysis , mechanical engineering , engineering
Scalar coupling constants have been computed using the EOM‐CCSD method for equilibrium structures of complexes stabilized by FH…P hydrogen bonds, as well as structures along the proton‐transfer coordinates of these complexes. Variations in the signs and absolute values of 1 J (FH), 1 h J (HP) and 2 h J (FP) have been analyzed and interpreted in terms of changing hydrogen bond type. Of the three phosphorus bases (phosphine, trimethylphosphine and phosphinine) investigated in this study, trimethylphosphine forms the strongest complex with FH, and has the largest two‐bond FP coupling constant. Among the relatively simple phosphorus bases, it would appear to be a leading candidate for experimental NMR study. Similarities and differences are noted between the corresponding coupling constants ( J ) and the reduced coupling constants ( K ) across FH…P and FH…N hydrogen bonds. Copyright © 2007 John Wiley & Sons, Ltd.