3hJ(15N-31P) spin-spin coupling contants across N-H•••O-P hydrogen bonds

被引:30
作者
Del Bene, JE [1 ]
Perera, SA
Bartlett, RJ
Elguero, J
Alkorta, I
López-Leonardo, C
Alajarin, M
机构
[1] Youngstown State Univ, Dept Chem, Youngstown, OH 44555 USA
[2] Univ Florida, Quantum Theory Project, Gainesville, FL 32611 USA
[3] CSIC, Inst Quim Med, E-28006 Madrid, Spain
[4] Univ Murcia, Fac Quim, Dept Quim Organ, E-30100 Murcia, Spain
关键词
D O I
10.1021/ja011755o
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Equation-of-motion coupled cluster singles and doubles (EOM-CCSD) calculations have been performed to evaluate three-bond N-15-P-31 coupling constants ((3h)J(N-P)) across N-H...O-P hydrogen bonds in model cationic and anionic complexes including NH4+:OPH, NH4+:OPH3, NH3:-O2PH2, NFH2:-O2PH2, and NF2H:-O2PH2. Three-bond coupling constants can be appreciable when the phosphorus is P(V), but are negligible with P(III). (3h)J(N-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-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-P), even though the N-P distances are longer than N-P distances in cyclic and open structures. In linear complexes, (3h)J(N-P) is dominated by the Fermi-contact term, which is distance dependent. Therefore, N-P (and hydrogen-bonding N-O) distances in these complexes can be determined from experimentally measured N-15-P-31 coupling constants.
引用
收藏
页码:6393 / 6397
页数:5
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