Reaction between the phosphinito bridged diplatinum species [(PHCy2 )Pt(μ-PCy2 )κ(2) P,O-μ-P(O)Cy2 Pt(PHCy2 )](Pt-Pt) (1), and (trimethylsilyl)acetylene at 273 K affords the σ-acetylide complex [(PHCy2 )(η(1) -Me3 SiC≡C)Pt(μ-PCy2 )Pt(PHCy2 )κP-P(OH)Cy2 ](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) ).

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

MASTRORILLI, Pietro
;
GALLO, Vito;TODISCO, Stefano;LATRONICO, Mario;
2016

Abstract

Reaction between the phosphinito bridged diplatinum species [(PHCy2 )Pt(μ-PCy2 )κ(2) P,O-μ-P(O)Cy2 Pt(PHCy2 )](Pt-Pt) (1), and (trimethylsilyl)acetylene at 273 K affords the σ-acetylide complex [(PHCy2 )(η(1) -Me3 SiC≡C)Pt(μ-PCy2 )Pt(PHCy2 )κP-P(OH)Cy2 ](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) ).
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11589/80004
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