title: (3h)J((15)N-(31)P) spin-spin coupling constants across N[bond]H....O[bond]P hydrogen bonds.
abstract: 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(N[bond]P)) across N[bond]H....O[bond]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(N[bond]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(N[bond]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(N[bond]P), even though the N[bond]P distances are longer than N[bond]P distances in cyclic and open structures. In linear complexes, (3h)J(N[bond]P) is dominated by the Fermi-contact term, which is distance dependent. Therefore, N[bond]P (and hydrogen-bonding N[bond]O) distances in these complexes can be determined from experimentally measured (15)N-(31)P coupling constants.
authors.affiliation: Department of Chemistry, Youngstown State University, Youngstown, Ohio 44555, USA. fr042008@ysub.ysu.edu
authors.forename: Janet E
authors.initials: JE
authors.lastname: Del Bene
authors.forename: S Ajith
authors.initials: SA
authors.lastname: Perera
authors.forename: Rodney J
authors.initials: RJ
authors.lastname: Bartlett
authors.forename: José
authors.initials: J
authors.lastname: Elguero
authors.forename: Ibon
authors.initials: I
authors.lastname: Alkorta
authors.forename: Carmen
authors.initials: C
authors.lastname: López-Leonardo
authors.forename: Mateo
authors.initials: M
authors.lastname: Alajarin