(3h)J((15)N-(31)P) spin-spin coupling constants across N[bond]H....O[bond]P hydrogen bonds

Equation-of-motion coupled cluster singles and doubles (EOM-CCSD) calculations have been performed to evaluate three-bond (15)N-(31)P coupling constants ((3h)J(Nbond]P)) across Nbond]H....Obond]P hydrogen bonds in model cationic and anionic complexes including NH(4)(+):OPH, NH(4)(+):OPH(3), NH(3):(-)O(2)PH(2), NFH(2):(-)O(2)PH(2), and NF(2)H:(-)O(2)PH(2). Three-bond coupling constants can be appreciable when the phosphorus is P(V), but are negligible with P(III). (3h)J(Nbond]P) values in complexes with cyclic or open structures are less than 1 Hz, a consequence of the nonlinear arrangement of N, H, O, and P atoms. For complexes with these structures, (3h)J(Nbond]P) may not be experimentally measurable. In contrast, complexes in which the N, H, O, and P atoms are collinear or nearly collinear have larger values of (3h)J(Nbond]P), even though the Nbond]P distances are longer than Nbond]P distances in cyclic and open structures. In linear complexes, (3h)J(Nbond]P) is dominated by the Fermi-contact term, which is distance dependent. Therefore, Nbond]P (and hydrogen-bonding Nbond]O) distances in these complexes can be determined from experimentally measured (15)N-(31)P coupling constants.