NH+-F hydrogen bonding in a fluorinated "proton sponge" derivative: integration of solution, solid-state, gas-phase, and computational studies.

We report detailed studies on the characterization of an intramolecular NH-F hydrogen bond formed within a fluorinated "proton sponge" derivative. An ammonium ion, generated from 8-fluoro-N,N-dimethylnaphthalen-1-amine, serves as a charged hydrogen bond donor to a covalently bound fluorine appropriately positioned on the naphthalene skeleton. Potentiometric titrations of various N,N-dimethylnaphthalen-1-amines demonstrate a significant increase in basicity when hydrogen bonding is possible. X-ray crystallography reveals that NH-F hydrogen bonding in protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine is heavily influenced by ion pairing in the solid state; bifurcated and trifurcated hydrogen bonds are formed depending on the counterion utilized. Compelling evidence of hydrogen bonding in the 8-fluoro-N,N-dimethylnaphthyl-1-ammonium cation is provided by gas-phase cryogenic vibrational photodissociation spectroscopy. Solution-phase infrared spectroscopy provides complementary results, and the frequencies of the N-H stretching mode in both phases are in excellent agreement with the computed vibrational spectra. NMR analysis of protonated 8-fluoro-N,N-dimethylnaphthalen-1-amine demonstrates significant H-F coupling between the N-H hydrogen and fluorine that cannot be attributed to long-range, through-bond interactions; the couplings correlate favorably with calculated values. The results obtained from these experiments are congruent with the formation of an NH-F hydrogen bond upon protonation of 8-fluoro-N,N-dimethylnaphthalen-1-amine.

[1]  Scott J. Miller,et al.  Vibrational characterization of simple peptides using cryogenic infrared photodissociation of H2-tagged, mass-selected ions. , 2011, Journal of the American Chemical Society.

[2]  Mark A. Johnson,et al.  Vibrational predissociation spectroscopy of the H2-tagged mono- and dicarboxylate anions of dodecanedioic acid , 2011 .

[3]  G. Berden,et al.  Effects of anions on the zwitterion stability of Glu, His and Arg investigated by IRMPD spectroscopy and theory , 2010 .

[4]  Jie Zhang,et al.  Trifluoromethanesulfonate Anion-linked Supramolecular Frameworks of Cucurbit[5]uril and Cucurbit[7]uril , 2010 .

[5]  J. Oomens,et al.  Structures of protonated dipeptides: the role of arginine in stabilizing salt bridges. , 2009, Journal of the American Chemical Society.

[6]  S. Scheiner.  Identification of spectroscopic patterns of CH...O H-bonds in proteins. , 2009, The journal of physical chemistry. B.

[7]  J. Elguero,et al.  A DFT and AIM analysis of the spin–spin couplings across the hydrogen bond in the 2‐fluorobenzamide and related compounds , 2009, Magnetic resonance in chemistry : MRC.

[8]  H. Takemura,et al.  C–F⋯HO hydrogen bond in 8-fluoro-4-methyl-1-naphthol , 2009 .

[9]  L. Hennig,et al.  Fluorine hydrogen short contacts and hydrogen bonds in substituted benzamides , 2009 .

[10]  K. Asmis,et al.  Messenger-tagging electrosprayed ions: vibrational spectroscopy of suberate dianions. , 2009, The journal of physical chemistry. A.

[11]  S. Scheiner,et al.  Spectroscopic and structural signature of the CH-O hydrogen bond. , 2008, The journal of physical chemistry. A.

[12]  Scott J. Miller,et al.  Functional analysis of an aspartate-based epoxidation catalyst with amide-to-alkene peptidomimetic catalyst analogues. , 2008, Angewandte Chemie.

[13]  J. Watts,et al.  Structure and Properties of Perfluoroalkylated Phthalocyanines. A Theoretical Study , 2008 .

[14]  M. Bortoluzzi,et al.  A DFT study on the interactions between the [Pt(H2O)(terpy)]2+ cation and the triflate and perchlorate counter-anions , 2008 .

[15]  J. Sessler,et al.  The largest 15N-15N coupling constant across an NHN hydrogen bond. , 2008, Angewandte Chemie.

[16]  Z. Tian,et al.  Hydrogen-deuterium exchange and selective labeling of deprotonated amino acids and peptides in the gas phase. , 2008, Journal of the American Chemical Society.

[17]  S. Scheiner,et al.  Underlying source of the relation between polypeptide conformation and strength of NH···O hydrogen bonds , 2007 .

[18]  Jos Oomens,et al.  Infrared spectroscopy of arginine cation complexes: direct observation of gas-phase zwitterions. , 2007, The journal of physical chemistry. A.

[19]  L. Radom,et al.  An evaluation of harmonic vibrational frequency scale factors. , 2007, The journal of physical chemistry. A.

[20]  T. Rizzo,et al.  Spectroscopic signatures of gas-phase helices: Ac-Phe-(Ala)5-Lys-H+ and Ac-Phe-(Ala)10-Lys-H+. , 2007, Journal of the American Chemical Society.

[21]  V. G. Beylin,et al.  Practical Alternative Synthesis of 1-(8-Fluoro-naphthalen-1-yl)piperazine , 2007 .

[22]  S. Scheiner,et al.  Theoretical evidence for a NH...XC blue-shifting hydrogen bond: complexes pairing monohalomethanes with HNO. , 2007, The journal of physical chemistry. A.

[23]  B. Trofimov,et al.  Bifurcated hydrogen‐bonding effect on the shielding and coupling constants in trifluoroacetyl pyrroles as studied by 1H, 13C and 15N NMR spectroscopy and DFT calculations , 2007, Magnetic resonance in chemistry : MRC.

[24]  Z. Tian,et al.  Organic gas-phase ion chemistry , 2006 .

[25]  S. U. Son,et al.  Charge-Assisted Hydrogen Bonding and Other Noncovalent Interactions in the Self-Assembly of the Organometallic Building Block [(η6-hydroquinone)Rh(P(OPh)3)2]+ with a Range of Counteranions , 2006 .

[26]  M. F. Bush,et al.  Infrared spectroscopy of hydrated amino acids in the gas phase: protonated and lithiated valine. , 2006, Journal of the American Chemical Society.

[27]  L. Sobczyk,et al.  [NHN]+ hydrogen bonding in protonated 1,8-bis(dimethylamino)-2,7-dimethoxynaphthalene. X-ray diffraction, infrared, and theoretical ab initio and DFT studies. , 2005, The journal of physical chemistry. A.

[28]  J. Elguero,et al.  One-bond spin-spin coupling constants of X-1H proton donors in complexes with X-H-Y hydrogen bonds, for X = 13C, 15N, 17O, and 19F: predictions, comparisons, and relationships among 1J X-H, 1K X-H, and X-H distances. , 2004, Journal of the American Chemical Society.

[29]  G. Cruciani,et al.  Hydrogen bonding interactions of covalently bonded fluorine atoms: from crystallographic data to a new angular function in the GRID force field. , 2004, Journal of medicinal chemistry.

[30]  A. Bacchi,et al.  The Structural Role of the Triflate Anion in the Non-Covalent Silver Polymer [Ag(LOH)2(CF3SO3)(CH3CN)] {LOH = α-(4-Pyridyl)benzhydrol} , 2004 .

[31]  T. Shinmyozu,et al.  9‐Fluoro‐18‐hydroxy‐[3.3]metacyclophane: Synthesis and Estimation of a C−F···H−O Hydrogen Bond , 2004 .

[32]  S. Smirnov,et al.  Low-temperature NMR studies of the structure and dynamics of a novel series of acid-base complexes of HF with collidine exhibiting scalar couplings across hydrogen bonds. , 2003, Journal of the American Chemical Society.

[33]  Chick C. Wilson,et al.  From weak interactions to covalent bonds: a continuum in the complexes of 1,8-bis(dimethylamino)naphthalene. , 2003, Journal of the American Chemical Society.

[34]  T. Morton,et al.  Carbocation rearrangements of trimethylsilyl adducts of saturated acyclic C5–C7 ketones in the gas phase , 2002 .

[35]  L. Sobczyk,et al.  X-ray diffraction and IR-spectroscopic studies on protonated 4-amino-1,8-bis(dimethylamino)naphthalene , 2002 .

[36]  S. Kass,et al.  Formation of a 1-bicyclo[1.1.1]pentyl anion and an experimental determination of the acidity and C-H bond dissociation energy of 3-tert-butylbicyclo[1.1.1]pentane. , 2002, Journal of the American Chemical Society.

[37]  M. Pecul,et al.  The 19F–1H coupling constants transmitted through covalent, hydrogen bond, and van der Waals interactions , 2001 .

[38]  C. Perrin,et al.  Symmetry of N-H-N hydrogen bonds in 1,8-bis(dimethylamino)naphthalene.H+ and 2,7-dimethoxy-1,8-bis(dimethylamino)naphthalene.H+. , 2001, Journal of the American Chemical Society.

[39]  J. Deisenhofer,et al.  Structural Mechanism for Statin Inhibition of HMG-CoA Reductase , 2001, Science.

[40]  T. Morton,et al.  Intramolecular fluorine migration via four-member cyclic transition states , 2000, The Journal of organic chemistry.

[41]  S. T. Howard.  Relationship between Basicity, Strain, and Intramolecular Hydrogen-Bond Energy in Proton Sponges , 2000 .

[42]  R. Bartlett,et al.  Predicted NMR Coupling Constants Across Hydrogen Bonds: A Fingerprint for Specifying Hydrogen Bond Type? , 2000 .

[43]  J. Janin,et al.  Catalytic mechanism of nucleoside diphosphate kinase investigated using nucleotide analogues, viscosity effects, and X-ray crystallography. , 1999, Biochemistry.

[44]  Chick C. Wilson,et al.  Charge Density Distribution in the “Proton Sponge” Compound 1,8-Bis(dimethylamino)naphthalene , 1999 .

[45]  S. Withers,et al.  Sugar ring distortion in the glycosyl-enzyme intermediate of a family G/11 xylanase. , 1999, Biochemistry.

[46]  A. Davis,et al.  Hydrogen Bonding, Hydrophobic Interactions, and Failure of the Rigid Receptor Hypothesis. , 1999, Angewandte Chemie.

[47]  T. Lectka,et al.  Strong Hydrogen Bonding to the Amide Nitrogen Atom in an "Amide Proton Sponge": Consequences for Structure and Reactivity. , 1999, Angewandte Chemie.

[48]  S J Remington,et al.  Crystal structures of Escherichia coli glycerol kinase variant S58-->W in complex with nonhydrolyzable ATP analogues reveal a putative active conformation of the enzyme as a result of domain motion. , 1999, Biochemistry.

[49]  S. Smirnov,et al.  Nuclear Scalar Spin–Spin Coupling Reveals Novel Properties of Low‐Barrier Hydrogen Bonds in a Polar Environment , 1999 .

[50]  T. Shaler,et al.  Conformations of β-Fluorophenetole and Their Reactivities Studied by Supersonic Jet/REMPI Spectroscopy , 1999 .

[51]  M. Gdaniec,et al.  Three-Center CF···HN Intramolecular Hydrogen Bonding in the 2,6-Bis(2,6-difluorophenyl)piperidine Systems1 , 1998 .

[52]  E. Grech,et al.  SOLID-STATE NMR AND X-RAY DIFFRACTION STUDIES OF IONIC COMPLEX OF 1,8-BIS(DIMETHYLAMINO)NAPHTHALENE (DMAN) WITH PICROLONIC ACID , 1997 .

[53]  D. Moras,et al.  A 'specificity' pocket inferred from the crystal structures of the complexes of aldose reductase with the pharmaceutically important inhibitors tolrestat and sorbinil. , 1997, Structure.

[54]  Gautam R. Desiraju,et al.  The C-h···o hydrogen bond:  structural implications and supramolecular design. , 1996, Accounts of chemical research.

[55]  Dedreia Tull,et al.  Crystallographic observation of a covalent catalytic intermediate in a β-glycosidase , 1996, Nature Structural Biology.

[56]  T. Shaler,et al.  Fluorine Shifts in Gaseous Cations. Analogs of Wagner-Meerwein Rearrangements , 1994 .

[57]  S. Kass,et al.  Stereospecificity in the Gas Phase. Formation and Characterization of Configurationally Stable Cyclopropyl Anions , 1994 .

[58]  R. Biekofsky,et al.  Analysis of long‐range through‐space couplings via an intramolecular hydrogen bond , 1993 .

[59]  Xueheng Cheng,et al.  Three-Membered Cyclic Fluoronium Ions in Gaseous Ion-Neutral Complexes , 1992 .

[60]  M. Summers,et al.  Novel observation of NH--S(Cys) hydrogen-bond-mediated scalar coupling in cadmium-113 substituted rubredoxin from Pyrococcus furiosus , 1992 .

[61]  S. Kass,et al.  Reactions of strong bases with vinyl fluoride formation and characterization of 1-fluorovinyl anion and the fluoride-acetylene hydrogen-bonded complex , 1992, Journal of the American Society for Mass Spectrometry.

[62]  Gautam R. Desiraju,et al.  The C-H.cntdot..cntdot..cntdot.O hydrogen bond in crystals: what is it? , 1991 .

[63]  Professor Dr. George A. Jeffrey,et al.  Hydrogen Bonding in Biological Structures , 1991, Springer Berlin Heidelberg.

[64]  R Radhakrishnan,et al.  Crystal Structure of the Covalent Complex Formed by a Peptidyl Alpha,Alpha-Difluoro-Beta-Keto Amide with Porcine Pancreatic Elastase at 1.78-Angstroms Resolution , 1989 .

[65]  T. Zeegers-Huyskens,et al.  Solvent effect on the intramolecular hydrogen bond strength and on the isotopic ratio .nu.NH+/.nu.ND+ in a trisubstituted Mannich base , 1987 .

[66]  T. Winkler,et al.  Weitreichende Kernspin‐Kopplungen in 2‐Fluorbenzamiden II. [15N]‐2‐Fluorbenzamid , 1975 .

[67]  T. Winkler,et al.  Weitreichende Kopplung zwischen Protonen und Fluor in 2-Fluorbenzamiden , 1974 .

[68]  T. Schaefer,et al.  Hydrogen bonding and long-range proton coupling constants in some ortho disubstituted aniline derivatives. Intramolecular proton exchange and degree of nonplanarity of the amino group , 1970 .

[69]  A. Bondi.  van der Waals Volumes and Radii , 1964 .

[70]  L. G. Chatten,et al.  Relationship between pKb(H2O) of Organic Compounds and E 1∕2 Values in Several Nonaqueous Solvents. , 1962 .

[71]  C. A. Streuli.  Titration Characteristics of Organic Bases in Nitromethane , 1959 .

[72]  G. Sheldrick.  A short history of SHELX. , 2008, Acta crystallographica. Section A, Foundations of crystallography.

[73]  T. Morton,et al.  Taming halonium metathesis , 2003 .

[74]  C. Perrin,et al.  Symmetry of NHN hydrogen bonds in solution , 2003 .

[75]  A. Vasella,et al.  Glycosylidene Carbenes part 26. The intramolecular F…︁HO hydrogen bond of 1,3‐diaxial 3‐fluorocyclohexanols , 1998 .

[76]  T. Steiner.  Weak hydrogen bonding. Part 1. Neutron diffraction data of amino acid Cα–H suggest lengthening of the covalent C–H bond in C–H ⋯ O interactions , 1995 .

[77]  W. C. Lineberger,et al.  Pulsed methods for cluster ion spectroscopy , 1987 .

[78]  M. Musiani,et al.  N-Permethylation of Primary and Secondary Aromatic Amines , 1980 .

[79]  J. Cornelisse,et al.  Photoreactions of Aromatic Compounds. XXXVII.1 Photosubstitution Reactions of Nitronaphthalene Derivatives , 1977 .

[80]  M. Dewar,et al.  Substituent Effects. VIII.1 Synthesis of Substituted α- and β-Fluoronaphthalenes2 , 1967 .

[81]  H. Hall.  Potentiometric Determination of the Base Strength of Amines in Non-protolytic Solvents , 1956 .