Influence of the d orbital occupation on the nature and strength of copper cation-pi interactions: threshold collision-induced dissociation and theoretical studies.

Threshold collision-induced dissociation techniques are employed to determine the bond dissociation energies of a wide variety of copper cation-pi complexes, Cu(+)(pi-ligand), where pi-ligand = benzene, flurobenzene, chlorobenzene, bromobenzene, iodobenzene, phenol, toluene, anisole, pyrrole, N-methylpyrrole, indole, naphthalene, aniline, N-methylaniline, and N,N-dimethylaniline. The primary and lowest energy dissociation pathway corresponds to the endothermic loss of the intact neutral pi-ligand for all complexes except those to N-methylpyrrole, indole, aniline, N-methylaniline, and N,N-dimethylaniline. In the latter complexes, the primary dissociation pathway corresponds to loss of the intact ligand accompanied by charge transfer, thereby producing a neutral copper atom and ionized pi-ligand. Fragmentation of the pi-ligands is also observed at elevated energies in several cases. Theoretical calculations at the B3LYP/6-311G(d,p) level of theory are used to determine the structures, vibrational frequencies, and rotational constants of these complexes. Multiple low-energy conformers are found for all of the copper cation-pi complexes. Theoretical bond dissociation energies are determined from single point energy calculations at the B3LYP/6-311+G(3df,2p) level of theory using the B3LYP/6-311G(d,p) optimized geometries. The agreement between theory and experiment is very good for most complexes. The nature and strength of the binding in these copper cation-pi complexes are studied and compared with the corresponding cation-pi complexes to Na(+). Natural bond orbital analyses are carried out to examine the influence of the d orbital occupation on copper cation-pi interactions.

[1]  M. Rodgers,et al.  Cation-π interactions with a π-excessive nitrogen heterocycle: Structures and absolute binding energies of alkali metal cation–pyrrole complexes , 2007 .

[2]  M. Yáñez,et al.  Cu+ association to some Ph–X (X = OH, NH2, CHO, COOH, CF3) phenyl derivatives.: A comparison with Li+ complexes , 2006 .

[3]  Nick C. Polfer,et al.  IRMPD spectroscopy of metal-ion/tryptophan complexes. , 2006, Physical chemistry chemical physics : PCCP.

[4]  J. Oomens,et al.  IR-spectroscopic characterization of acetophenone complexes with Fe+, Co+, and Ni+ using free-electron-laser IRMPD. , 2006, The journal of physical chemistry. A.

[5]  Nick C. Polfer,et al.  Infrared spectroscopy of phenylalanine Ag(I) and Zn(II) complexes in the gas phase. , 2006, Journal of the American Chemical Society.

[6]  Q. Guo,et al.  Cation–π interactions of Cu+ , 2005 .

[7]  M. Rodgers,et al.  Cation-pi interactions with a model for the side chain of tryptophan: structures and absolute binding energies of alkali metal cation-indole complexes. , 2005, The journal of physical chemistry. A.

[8]  J. Oomens,et al.  Infrared spectroscopy of gas-phase Cr+ coordination complexes: determination of binding sites and electronic states. , 2005, Journal of the American Chemical Society.

[9]  H. Schlegel,et al.  Static and Dynamic Polarizabilities of Conjugated Molecules and Their Cations , 2004 .

[10]  R. Grimm,et al.  Complexation of Gas-Phase Metal Ions with Furan: Experimental and Quantum Chemical Binding Energies , 2004 .

[11]  M. Rodgers,et al.  Cation-pi interactions: structures and energetics of complexation of Na+ and K+ with the aromatic amino acids, phenylalanine, tyrosine, and tryptophan. , 2004, Journal of the American Chemical Society.

[12]  J. Oomens,et al.  The site of Cr+ attachment to gas-phase aniline from infrared spectroscopy. , 2004, Journal of the American Chemical Society.

[13]  K. Ohkubo,et al.  Quantitative evaluation of d-pi interaction in copper(I) complexes and control of copper(I)-dioxygen reactivity. , 2004, Chemistry.

[14]  J. Abboud,et al.  Lithium-cation/pi complexes of aromatic systems. The effect of increasing the number of fused rings. , 2003, Journal of the American Chemical Society.

[15]  M. Rodgers,et al.  Cation-π interactions with a model for an extended π network , 2003 .

[16]  M. Rodgers,et al.  Influence of substituents on cation-π interactions. 2 - Absolute binding energies of alkali metal cation-fluorobenzene complexes determined by threshold collision-induced dissociation and theoretical studies , 2002 .

[17]  R. Dunbar.  Binding of Transition-Metal Ions to Curved π Surfaces: Corannulene and Coronene† , 2002 .

[18]  R. Dunbar.  Metal Cation Binding to Phenol: DFT Comparison of the Competing Sites , 2002 .

[19]  R. Dunbar,et al.  Reactivity and binding energies of transition metal halide ions with benzene , 2002, Journal of the American Society for Mass Spectrometry.

[20]  M. Rodgers,et al.  Sigma versus Pi Interactions in Alkali Metal Ion Binding to Azoles: Threshold Collision-Induced Dissociation and ab Initio Theory Studies , 2002 .

[21]  R. Dunbar,et al.  Cation-pi interactions and the gas-phase thermochemistry of the Na(+)/phenylalanine complex. , 2001, Journal of the American Chemical Society.

[22]  P. Armentrout,et al.  Guided ion beam study of collision-induced dissociation dynamics: integral and differential cross sections , 2001 .

[23]  V. Ryzhov,et al.  Cation-π effects in the complexation of Na+ and K+ with Phe, Tyr, and Trp in the gas phase , 2000, Journal of the American Society for Mass Spectrometry.

[24]  P. B. Armentrout,et al.  Absolute Binding Energies of Alkali-Metal Cation Complexes with Benzene Determined by Threshold Collision-Induced Dissociation Experiments and ab Initio Theory , 2000 .

[25]  R. Dunbar.  Complexation of Na+ and K+ to Aromatic Amino Acids: A Density Functional Computational Study of Cation-π Interactions , 2000 .

[26]  P. B. Armentrout,et al.  An Absolute Sodium Cation Affinity Scale: Threshold Collision-Induced Dissociation Experiments and ab Initio Theory , 2000 .

[27]  S. Klippenstein,et al.  Binding Energies of Gas-Phase Metal Ions with Pyrrole: Experimental and Quantum Chemical Results , 2000 .

[28]  D. A. Dougherty,et al.  Cation-π interactions in structural biology , 1999 .

[29]  Corey J. Weinheimer,et al.  Size selectivity by cation–π interactions: Solvation of K+ and Na+ by benzene and water , 1999 .

[30]  V. Ryzhov,et al.  Interactions of Phenol and Indole with Metal Ions in the Gas Phase: Models For Tyr and Trp Side-Chain Binding , 1999 .

[31]  Wolfram Koch,et al.  How do coinage metal ions bind to benzene , 1999 .

[32]  D. A. Dougherty,et al.  From ab initio quantum mechanics to molecular neurobiology: a cation-pi binding site in the nicotinic receptor. , 1998, Proceedings of the National Academy of Sciences of the United States of America.

[33]  O. Donini,et al.  Development of modified force field for cation–amino acid interactions: Ab initio‐derived empirical correction terms with comments on cation–π interactions , 1998 .

[34]  P. Armentrout,et al.  Statistical modeling of competitive threshold collision-induced dissociation , 1998 .

[35]  J. C. Ma,et al.  The Cationminus signpi Interaction. , 1997, Chemical reviews.

[36]  P. B. Armentrout,et al.  Statistical modeling of collision-induced dissociation thresholds , 1997 .

[37]  D A Dougherty,et al.  Cation-pi interactions in aromatics of biological and medicinal interest: electrostatic potential surfaces as a useful qualitative guide. , 1996, Proceedings of the National Academy of Sciences of the United States of America.

[38]  Sandro Mecozzi,et al.  Cation−π Interactions in Simple Aromatics: Electrostatics Provide a Predictive Tool , 1996 .

[39]  D. A. Dougherty,et al.  Cation-π Interactions in Chemistry and Biology: A New View of Benzene, Phe, Tyr, and Trp , 1996, Science.

[40]  P. B. Armentrout,et al.  Thermochemistry of transition metal benzene complexes: Binding energies of M(C6H6)x + (x = 1, 2) for M = Ti to Cu , 1995 .

[41]  J. V. Lenthe,et al.  State of the Art in Counterpoise Theory , 1994 .

[42]  A. Karlin,et al.  Electrostatic potential of the acetylcholine binding sites in the nicotinic receptor probed by reactions of binding-site cysteines with charged methanethiosulfonates. , 1994, Biochemistry.

[43]  J. Thornton,et al.  Amino/aromatic interactions in proteins: is the evidence stacked against hydrogen bonding? , 1994, Journal of molecular biology.

[44]  P. B. Armentrout,et al.  Solvation of Transition Metal Ions by Water. Sequential Binding Energies of M+(H2O)x (x = 1-4) for M = Ti to Cu Determined by Collision-Induced Dissociation , 1994 .

[45]  P. Armentrout,et al.  Stepwise solvation enthalpies of protonated water clusters: collision-induced dissociation as an alternative to equilibrium studies , 1993 .

[46]  Farooq A. Khan,et al.  Sequential bond energies of chromium carbonyls (Cr(CO)x+, x = 1-6) , 1993 .

[47]  A. Karlin.  Structure of nicotinic acetylcholine receptors , 1993, Current Opinion in Neurobiology.

[48]  J. Simons,et al.  Understanding heterolytic bond cleavage , 1992 .

[49]  C. Bauschlicher,et al.  Theoretical study of transition-metal ions bound to benzene , 1992 .

[50]  A. Fersht,et al.  Histidine residues at the N- and C-termini of alpha-helices: perturbed pKas and protein stability. , 1992, Biochemistry.

[51]  M. Ultsch,et al.  Human growth hormone and extracellular domain of its receptor: crystal structure of the complex. , 1992, Science.

[52]  Michael A. Duncan,et al.  Charge-transfer photochemistry in ion-molecule cluster complexes of silver , 1991 .

[53]  L Serrano,et al.  Aromatic-aromatic interactions and protein stability. Investigation by double-mutant cycles. , 1991, Journal of molecular biology.

[54]  Kenneth J. Miller,et al.  Additivity methods in molecular polarizability , 1990 .

[55]  B. Guo,et al.  The clustering reactions of benzene with sodium and lead ions , 1990 .

[56]  P. Armentrout,et al.  Effect of internal excitation on the collision-induced dissociation and reactivity of Co2+ , 1990 .

[57]  B. Matthews,et al.  Enhanced protein thermostability from designed mutations that interact with α-helix dipoles , 1990, Nature.

[58]  R. Taft,et al.  Free energies of cation-molecule complex formation and cation-solvent transfers , 1990 .

[59]  A. R. Ellis,et al.  A study of the phenyl radical by vacuum ultraviolet photoelectron spectroscopy , 1987 .

[60]  R. Hettich,et al.  Spectroscopic and thermodynamic investigations of transition-metal cluster ions in the gas phase photodissociation of MFe+ , 1987 .

[61]  P. Armentrout,et al.  Collision-induced dissociation of vanadium monoxide ion , 1986 .

[62]  P. Armentrout,et al.  Translational energy dependence of Ar++XY→ArX++Y (XY=H2,D2,HD) from thermal to 30 eV c.m. , 1985 .

[63]  D. Golden,et al.  Hydrocarbon Bond Dissociation Energies , 1983 .

[64]  M. Bowers,et al.  THEORY OF TRANSLATIONALLY DRIVEN REACTIONS , 1979 .

[65]  S. Stein,et al.  On the use of exact state counting methods in RRKM rate calculations , 1977 .

[66]  D. Gerlich,et al.  Integral cross sections for ion—molecule reactions. I. The guided beam technique , 1974 .

[67]  Terry Beyer,et al.  Algorithm 448: number of multiply-restricted partitions , 1973, CACM.

[68]  S. Stein,et al.  Accurate evaluation of internal energy level sums and densities including anharmonic oscillators and hindered rotors , 1973 .

[69]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[70]  J. Sunner,et al.  Ion-solvent molecule interactions in the gas phase , 1968 .

[71]  T. F. Palmer,et al.  The Vertical Ionization Potentials of Phenyl and Phenoxy Radicals , 1964 .

[72]  M. Rodgers,et al.  Influence of substituents on cation-π interactions , 2003 .

[73]  Yuan-Ping Pang,et al.  Structure of acetylcholinesterase complexed with the nootropic alkaloid, (–)-huperzine A , 1997, Nature Structural Biology.

[74]  W. R. Wadt,et al.  Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals , 1985 .

[75]  A. D. McLean,et al.  Molecular orbital predictions of the vibrational frequencies of some molecular ions. , 1985, The Journal of chemical physics.

[76]  R. Woodin,et al.  Binding of lithium(1+) ion to Lewis bases in the gas phase. Reversals in methyl substituent effects for different reference acids , 1978 .