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

页码：7964 / 7969

页数：6

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