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

共 50 条

[31] Complete Characterization of the 3D Properties of the CCR5 Antagonist Vicriviroc through DFT Calculations, NMR Spectroscopy, and X-ray Analysis
Legnani, Laura
Colombo, Diego
Villa, Stefania
Meneghetti, Fiorella
Castellano, Carlo
Gelain, Arianna
Albini, Franca Marinone
Toma, Lucio
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, 2012 (26) : 5069 - 5074
[32] The Mechanism of the Stereospecific Intramolecular Arylation of Lithiated Ureas: The Role of Li plus Probed by Electronic Structure Calculations, and by NMR and IR Spectroscopy
Grainger, Damian M.
Smith, Alison Campbell
Vincent, Mark A.
Hillier, Ian H.
Wheatley, Andrew E. H.
Clayden, Jonathan
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, 2012 (04) : 731 - 743
[33] Direct NMR observation and DFT calculations of a hydrogen bond at the active site of a 44 kDa enzyme
Alexander Eletsky
Tim Heinz
Osvaldo Moreira
Alexander Kienhöfer
Donald Hilvert
Konstantin Pervushin
Journal of Biomolecular NMR, 2002, 24 : 31 - 39
[34] Structure and Hydrogen Bonding Interactions in Methoxysalicylaldehyde Thiosemicarbazone Derivatives in Solution by NMR and DFT Methods
Novak, Predrag
Piculjan, Katarina
Hrenar, Tomica
Smrecki, Vilko
CROATICA CHEMICA ACTA, 2009, 82 (02) : 477 - 482
[35] Structural Determination of Antioxidant and Anticancer Flavonoid Rutin in Solution through DFT Calculations of 1H NMR Chemical Shifts
De Souza, Leonardo A.
Da Silva, Haroldo C.
De Almeida, Wagner B.
CHEMISTRYOPEN, 2018, 7 (11): : 902 - 913
[36] Hydrogen bonding and molecular association in 2-(quinuclidinium)-butyric acid bromide hydrate studied by X-ray diffraction, DFT calculations, FTIR and NMR spectroscopy, and potentiometric titration
Dega-Szafran, Z.
Katrusiak, A.
Szafran, M.
Barczynski, P.
JOURNAL OF MOLECULAR STRUCTURE, 2010, 975 (1-3) : 357 - 366
[37] Conformational Preferences of cis-1,3-Cyclopentanedicarboxylic Acid and Its Salts by 1H NMR Spectroscopy: Energetics of Intramolecular Hydrogen Bonds in DMSO
Emenike, Bright U.
Carroll, William R.
Roberts, John D.
JOURNAL OF ORGANIC CHEMISTRY, 2013, 78 (05) : 2005 - 2011
[38] Determining the strengths of hydrogen bonds in solid-state ammonia and urea: Insight from periodic DFT calculations
Morrison, CA
Siddick, MM
CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (03) : 628 - 634
[39] 1H NMR Studies of Intramolecular OH/OH Hydrogen Bonds via Titratable Isotope Shifts
Kolahdouzan, Kavoos
Ogba, O. Maduka
O'Leary, Daniel J.
JOURNAL OF ORGANIC CHEMISTRY, 2022, 87 (03) : 1732 - 1744
[40] 1-Carboxyethylpyridinium-4-carboxylate inner salt studied by X-ray diffraction, DFT calculations, vibrational and NMR spectroscopy
Barczynski, P.
Katrusiak, A.
Dega-Szafran, Z.
Szafran, M.
JOURNAL OF MOLECULAR STRUCTURE, 2009, 937 (1-3) : 85 - 94

← 1 2 3 4 5 →