Uncovering Intramolecular π-Type Hydrogen Bonds in Solution by NMR Spectroscopy and DFT Calculations

被引：16
|
作者：
Mastrorilli, Piero [1 ]
Gallo, Vito [1 ]
Todisco, Stefano [1 ]
Latronico, Mario [1 ]
Saielli, Giacomo [2 ]
机构：
[1] Politecn Bari, DICATECh, Via Orabona 4, I-70125 Bari, Italy
[2] CNR, Ist Tecnol Membrane, Unita Padova, Via Marzolo 1, I-35131 Padua, Italy
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 23期
关键词：
alkyne ligands; density functional calculations; hydrogen bonds; NMR spectroscopy; phosphane ligands; platinum; DENSITY-FUNCTIONAL CALCULATIONS; MOLECULAR TORSION BALANCE; SPIN COUPLING-CONSTANTS; BRIDGED PT(I) COMPLEX; PT-I COMPLEX; APPROXIMATION; CRYSTAL; CONFORMATIONS; MULTINUCLEAR; PROTONATION;
D O I：
10.1002/chem.201600078
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Reaction between the phosphinito bridged diplatinum species [(PHCy2)Pt(mu-PCy2){kappa P-2,O-mu-P(O)Cy-2}Pt(PHCy2)](Pt-Pt) (1), and (trimethylsilyl) acetylene at 273K affords the sigma-acetylide complex [(PHCy2)(eta(1)-Me3SiC C)Pt(mu-PCy2)Pt(PHCy2){kappa P-P(OH)Cy-2}](Pt-Pt) (2) featuring an intramolecular pi-type hydrogen bond. Scalar and dipolar couplings in- volving the POH proton were detected by 2D NMR experiments. Relativistic DFT calculations of the geometry, relative energy, and NMR properties of model systems of 2 confirmed the structural assignment and allowed the energy of the pi-type hydrogen bond to be estimated (ca. 22 kJ mol(-1)).
引用
收藏
页码：7964 / 7969
页数：6
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