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Uncovering Intramolecular π‐Type Hydrogen Bonds in Solution by NMR Spectroscopy and DFT Calculations
Author(s) -
Mastrorilli Piero,
Gallo Vito,
Todisco Stefano,
Latronico Mario,
Saielli Giacomo
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600078
Subject(s) - intramolecular force , chemistry , acetylene , hydrogen bond , nuclear magnetic resonance spectroscopy , acetylide , trimethylsilyl , crystallography , hydrogen , computational chemistry , stereochemistry , molecule , medicinal chemistry , organic chemistry
Reaction between the phosphinito bridged diplatinum species [(PHCy 2 )Pt(μ‐PCy 2 ){κ 2 P,O‐μ‐P(O)Cy 2 }Pt(PHCy 2 )](Pt–Pt) ( 1 ), and (trimethylsilyl)acetylene at 273 K affords the σ‐acetylide complex [(PHCy 2 )(η 1 ‐Me 3 SiC≡C)Pt(μ‐PCy 2 )Pt(PHCy 2 ){κP‐P(OH)Cy 2 }](Pt–Pt) ( 2 ) featuring an intramolecular π‐type hydrogen bond. Scalar and dipolar couplings involving 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 π‐type hydrogen bond to be estimated (ca. 22 kJ mol −1 ).