Uncovering Intramolecular π-Type Hydrogen Bonds in Solution by NMR Spectroscopy and DFT Calculations.
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) ).
Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica (DICATECh), Politecnico di Bari, via Orabona 4, 70125, Bari, Italy. p.mastrorilli@poliba.it.
Piero
0000-0001-8841-458X
P
Mastrorilli
Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica (DICATECh), Politecnico di Bari, via Orabona 4, 70125, Bari, Italy.
Vito
0000-0003-2926-3106
V
Gallo
Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica (DICATECh), Politecnico di Bari, via Orabona 4, 70125, Bari, Italy.
Stefano
S
Todisco
Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica (DICATECh), Politecnico di Bari, via Orabona 4, 70125, Bari, Italy.
Mario
0000-0002-8626-5901
M
Latronico
CNR, Istituto per la Tecnologia delle Membrane, Unità di Padova, via Marzolo, 1-35131, Padova, Italy.
Giacomo
0000-0003-3337-8395
G
Saielli
NMR spectroscopy; alkyne ligands; density functional calculations; hydrogen bonds; phosphane ligands; platinum