Coordination complexes exhibiting anion...pi interactions: synthesis, structure, and theoretical studies

The polydentate ligand 2,4,6-tris(dipyridin-2-ylamino)-1,3,5-triazine (dpyatriz) in combination with the Cu(ClO 4) 2/CuX 2 salt mixtures (X (-) = Cl (-), Br (-), or N 3 (-)) leads to the formation of molecular coordination aggregates with formulas [Cu 3Cl 3(dpyatriz) 2](ClO 4) 3 ( 2), [Cu 3Br 3(dpyatriz) 2](ClO 4) 3 ( 3), and [Cu 4(N 3) 4(dpyatriz) 2(DMF) 4(ClO 4) 2](ClO 4) 2 ( 4). These complexes consist of two dpyatriz ligands bridged via coordination to Cu (II) and disposed either face-to-face in an eclipsed manner ( 2 and 3) or parallel and mutually shifted in one direction. The copper ions complete their coordination positions with Cl (-) ( 2), Br (-) ( 3), or N 3 (-), ClO 4 (-), and N, N-dimethylformamide (DMF) ( 4) ligands. All complexes crystallize together with noncoordinate ClO 4 (-) groups that display anion...pi interactions with the triazine rings. These interactions have been studied by means of high level ab initio calculations and the MIPp partition scheme. These calculations have proven the ClO 4 (-)...[C 3N 3] interactions to be favorable and have revealed a synergistic effect from the combined occurrence of pi-pi stacking of triazine rings and the interaction of these moieties with perchlorate ions, as observed in the experimental systems.     

Dipyrrolyldiketone difluoroboron complexes: novel anion sensors with C-H...X- interactions

1,3-Dipyrrolyl-1,3-propanediones, synthesized from pyrroles and malonyl chloride, form BF2 complexes, which represent a new class of naked-eye sensors for halide and oxoanions. The association mode for the interactions of both the pyrrolyl NH and bridging CH protons with anions was confirmed by 1H NMR chemical shifts in CD2Cl2 and supported by theoretical studies. The binding constants (Ka) were estimated as 8.1x10(4), 2.0x10(3), 3.3x10(2), 1.3x10(4), and 80 M(-1) for F-, Cl-, Br-, H2PO4(-), and HSO4(-) by UV/Vis absorption spectral changes in CH2Cl2. Augmentation of Ka compared with dipyrrolylquinoxaline for H2PO4(-) is much larger than those for other anions. Contrary to other anions, F- quenches the emission almost completely, which was detected by the fluorescence spectrum as well as the naked-eye. In the case of the chloride anion complex, the formation of Cl(-)-bridged 1D networks, in which anion is associated with two BF2 complexes, is observed in the solid state.     

Noncovalent interactions between cytosine and SWCNT: curvature dependence of complexes via pi...pi stacking and cooperative CH...pi/NH...pi

Fragments of C24H12, adapted from a variety of armchair [(n,n), (n = 5, 7, and 8)] and zigzag [(m,0) (m = 8, 10, and 12)] single-walled carbon nanotube (SWCNT), are used to model corresponding SWCNTs with different diameters and electronic structures. The parallel binding mainly through pi...pi stacking interaction, as well as the perpendicular binding via cooperative NH...pi and CH...pi between cytosine and the fragments of SWCNT have been extensively investigated with a GGA type of DFT, PW91LYP/6-311++G(d,p). The eclipsed tangential (ET) conformation with respect to the six-membered ring of cytosine and the central ring of SWCNT fragments is less stable than the slipped tangential (ST) conformation for the given fragment; perpendicular conformations with NH2 and CH ends have higher negative binding energy than those with NH and CH ends. At PW91LYP/6-311++G(d,p) level, two tangential complexes are less bound than perpendicular complexes. However, as electron correlation is treated with MP2/6-311G(d,p) for PW91LYP/6-311++G(d,p) optimized complexes, it turns out there is an opposite trend that two tangential complexes become more stable than three perpendicular complexes. This result implies that electron correlation, a primary source to dispersion energy, has more significant contributions to the pi...pi stacking complexes than to the complexes via cooperative NH...pi and CH...pi interactions. In addition, it was found for the first time that binding energies for two tangential complexes become more negative with increasing nanotube diameter, while those for three perpendicular complexes have a weaker dependence on the curvature; i.e., binding energies are slightly less and less negative. The performance of a novel hybrid DFT, MPWB1K, was also discussed.     

High tetraalkylaluminate fluxionality in half-sandwich complexes of the trivalent rare-earth metals

Steric factors govern the formation of half-sandwich complexes (C5Me4R)Ln[N(SiHMe2)2]2 according to acid-base reactions utilising Ln[N(SiHMe2)2)3(thf)2 and substituted cyclopentadienes. Subsequent trimethylaluminium-promoted silylamide elimination produces the first half-sandwich bis(tetramethylaluminate) complexes (C5Me4R)Ln(AlMe4)2.     

Transferred hyperfine structure interactions in transition metal complexes

The transferred hyperfine interactions of octahedral transition metal complexes are discussed. The necessity of using a model which accounts for spin polarization is stressed. Results obtained by molecular orbital calculations using the multiple scattering method are presented for thirteen different octahedral clusters. The agreement with experiments is satisfactory except for the contact term where it is only moderately good. Even in the latter case, however, the calculations yield some valuable information, particularly concerning the core polarization contribution.     

Perturbing the structure of the 2-norbornyl cation through C-H...N and C-H...pi interactions

Quantum chemical studies on complexes of the 2-norbornyl cation with ammonia and benzene are described. These calculations demonstrate that the delocalized, bridged, nonclassical geometry that is usually favored for this carbocation can be perturbed significantly toward the normally less favorable classical geometry through appropriately oriented noncovalent interactions. Since such cations have been proposed as intermediates in enzyme and antibody catalyzed reactions, these results have implications for the nature of the cationic species that may be generated in the presence of electron-rich amino acid side chains of the sort that may be present in the active sites of biocatalysts.     

Effect of weak interactions on the H...H distance in stretched dihydrogen complexes

Computational and experimental results presented in this paper demonstrate that the H-H distance in stretched dihydrogen complexes can be hypersensitive to a variety of weak intra- and intermolecular interactions, including those with bulky ligands and solvent molecules, hydrogen-bonding interactions, or ion-pairing. Particularly, the complex IrH(H...H)Cl(2)(P(i)Pr(3))(2) which contains a stretched dihydrogen ligand in the crystalline form, as shown by neutron diffraction, is a trihydride in solution. The difference is due to the intermolecular Ir-Cl...H-Ir hydrogen bonding in the solid.     

A study of C-F...M(+) interaction: metal complexes of fluorine-containing cage compounds

The C-F...M(+) interaction was investigated by observation of the NMR spectroscopic changes and complexation studies between metal cations and the cage compounds 1 and 2 which have fluorobenzene units as donor atoms. As a result, the interaction was detected with all of the metal cations which form complexes with 1 and 2. The stability of the complexes of 1 and 2 was determined by the properties of the metal cations (ionic radii and degree of hydrolysis), not by the hard-soft nature of the cations. Crystallographic analyses of Tl(+) subset 1 and La(3+) subset 2 provided structural information (interatomic distances and bond angles), and the bond strengths, C-F...M(+), O...M(+), and N...M(+), were estimated by Brown's equation based on the structural data. Short C-F...Tl(+) (2.952-3.048 A) distances were observed in the complex Tl(+) subset 1. The C-F bond lengths in the complexes, Tl(+) subset 1 and La(3+) subset 2, are elongated compared to those of the metal-free compounds. Interestingly, no solvent molecules including water molecules were coordinated to La(3+) in the La(3+) subset 2. The stabilization energy of cation-dipole interaction was calculated on the basis of the data from X-ray crystallographic analysis, and it is roughly consistent with the (-)Delta H values estimated in solution. Thus, the C-F...M(+) interaction can be expressed by the cation-dipole interaction. This result explains the fact that compound 1 which has fluorine atom as hard donor strongly binds soft metals such as Ag(+) and Tl(+). Furthermore, it was concluded that the fluorobenzene unit has a poor electron-donating ability compared to that of ether oxygen or amine nitrogen, and thus the ratio of the coordination bond in C-F...M(+) is small. The specific and remarkable changes in the (1)H, (13)C, and (19)F NMR spectra were observed accompanied by the complexation between M(+) and the hosts 1 and 2. These spectral features are important tools for the investigation of the C-F...M(+) interaction. Furthermore, F.Tl(+) spin couplings were observed at room temperature in the Tl(+) subset 1, 2 (J(F-Tl) = 2914 Hz for Tl(+) subset 1 and 4558 Hz for Tl(+) subset 2), and these are clear and definitive evidence of the interaction.     

Solvent-induced aggregation through metal...metal/pi...pi interactions: large solvatochromism of luminescent organoplatinum(II) terpyridyl complexes

A dramatic color change and tremendous emission enhancement have been "switched on" upon increasing diethyl ether ratio in acetonitrile or acetone solution of [Pt(tpy)(CC-CCH)]OTf, attributed to the formation of Pt...Pt and pi-pi interactions. Two crystal forms (dark-green and red) of [Pt(tpy)(CC-CCH)]OTf, together with [Pt(tBu3-tpy)(CC-CCH)]OTf, show different crystal-packing modes as revealed by X-ray crystallography.     

Relationship between structure,fluxionality and racemization activity in organometallic derivatives of polyoxometalates

The catalytic activity of several organometallic derivatives of polyoxometalates, especially those of general formula [M₄O₁₆{M′(η⁶-arene)}₄] (M = Mo, W; M′ = Ru, Os), was evaluated in the racemization of secondary alcohols. A link between composition, fluxionality and catalytic activity was established.     

Testing electronic structure methods for describing intermolecular H...H interactions in supramolecular chemistry

In this article a wide variety of computational approaches (molecular mechanics force fields, semiempirical formalisms, and hybrid methods, namely ONIOM calculations) have been used to calculate the energy and geometry of the supramolecular system 2-(2'-hydroxyphenyl)-4-methyloxazole (HPMO) encapsulated in beta-cyclodextrin (beta-CD). The main objective of the present study has been to examine the performance of these computational methods when describing the short range H. H intermolecular interactions between guest (HPMO) and host (beta-CD) molecules. The analyzed molecular mechanics methods do not provide unphysical short H...H contacts, but it is obvious that their applicability to the study of supramolecular systems is rather limited. For the semiempirical methods, MNDO is found to generate more reliable geometries than AM1, PM3 and the two recently developed schemes PDDG/MNDO and PDDG/PM3. MNDO results only give one slightly short H...H distance, whereas the NDDO formalisms with modifications of the Core Repulsion Function (CRF) via Gaussians exhibit a large number of short to very short and unphysical H...H intermolecular distances. In contrast, the PM5 method, which is the successor to PM3, gives very promising results. Our ONIOM calculations indicate that the unphysical optimized geometries from PM3 are retained when this semiempirical method is used as the low level layer in a QM:QM formulation. On the other hand, ab initio methods involving good enough basis sets, at least for the high level layer in a hybrid ONIOM calculation, behave well, but they may be too expensive in practice for most supramolecular chemistry applications. Finally, the performance of the evaluated computational methods has also been tested by evaluating the energetic difference between the two most stable conformations of the host(beta-CD)-guest(HPMO) system.     

Hybrid host-guest complexes: directing the supramolecular structure through secondary host-guest interactions

A set of four hybrid host-guest complexes based on the inorganic crown ether analogue [H12W36O120]12- ({W36}) have been isolated and characterised. The cluster anion features a central rigid binding site made up of six terminal oxygen ligands and this motif allows the selective binding of a range of alkali and alkali-earth-metal cations. Here, the binding site was utilised to functionalise the metal oxide-based cavity by complexing a range of protonated primary amines within the recognition site. As a result, a set of four hybrid organic-inorganic host-guest complexes were obtained whereby the interactions are highly directed specifically within this cavity. The guest cations in these molecular assemblies range from the aromatic 2-phenethylamine (1) and 4-phenylbutylamine (2) to the bifunctional aromatic p-xylylene diamine (3) and the aliphatic, bifunctional 1,6-diaminohexane (4). Compounds 1-4 were structurally characterised by single-crystal X-ray diffraction, elemental analysis, flame atomic absorption spectroscopy, FTIR and bond valence sum calculations. This comparative study focuses on the supramolecular effects of the amine guest cations and investigates their structure-directing effects on the framework arrangement arising by locking the protonated amines within the cavity of the {W36} cluster. It was shown that parts of the organic guest cation protrude from the central binding cavity and the nature of this protruding organic "tail" directs the solid-state arrangement of compounds 1-4. Guest cations with a hydrophobic phenyl tail result in an antiparallel assembly of {W36} complexes arranged in a series of pillared layers. As a consequence, no direct supramolecular interactions between {W36} clusters are observed. In contrast, bifunctional guest cations with a secondary amino binding site act as molecular connectors and directly link two cluster units thus locking the supramolecular assembly in a tilted arrangement. This direct linking of {W36} anions results in the formation of an infinite supramolecular scaffold.     

Theoretical studies for Lewis acid-base interactions and C-H...O weak hydrogen bonding in various CO2 complexes

Comprehension of the basic concepts for the design of CO2-philic molecules is important due to the possibility for "green" chemistry in supercritical CO2 of substitute solvent systems. Lewis acid-base interactions and C-H...O weak hydrogen bonding were suggested as two key factors in the solubility of CO2-philic molecules. To isolate the stabilization energy of weak hydrogen bonding from the overall binding energy, high-level quantum mechanical calculations were performed for the van der Waals complexes of CO2 with methane, methylacetate, dimethylether, acetaldehyde, and 1,2-dimethoxyethane. Structures and energies were calculated at the MP2 level of theory using the 6-31+G(d) and aug-cc-pVDZ basis sets with basis set superposition error corrections. In addition, the single-point energies were calculated using recently developed multilevel methods. This study shows that the Lewis acid-base interaction has a significant impact on the complex stability compared to the C-H...O weak hydrogen bond. The additional stabilization energy of the cooperative weak hydrogen bond with alpha-proton of the carbonyl group was negligible on the enhancement of supercritical CO2 solubility. However, the stabilization energy was larger for the ether group, such that it may have an important role in increasing the supercritical CO2 solubility. Additional formation of cooperative weak hydrogen bonds may not further increase the solubility due to the stability reduction by steric hindrance.     

Cp*Rh complexes with pyridyloxazolines: synthesis, fluxionality and applications as asymmetric catalysts for Diels-Alder reactions

Half-sandwich complexes [RhCl(pymox)Cp*][SbF(6)](1-7)(pymox = pyridyloxazoline) have been synthesised as single diastereomers. Treatment of these with AgSbF(6) generates dications [Rh(OH(2))(pymox)Cp*](2+) which are fluxional at room temperature and which are enantioselective catalysts for the Diels-Alder reaction of methacrolein and cyclopentadiene. Treatment of the dication [Rh(OH(2))((i)Pr-pymox)Cp*](2+) with [X](-) gives [RhX((i)Pr-pymox)Cp*][SbF(6)](X = Br, I) as single diastereomers whilst reaction with 4-Mepy (4-methylpyridine) gives [Rh(4-Mepy)((i)Pr-pymox)Cp*][SbF(6)] as a mixture of diastereomers. Two complexes, [RhCl((i)Pr-pymox)Cp*][SbF(6)](3) and [RhCl(Bz-pymox)Cp*][SbF(6)](6) have been characterised by X-ray crystallography.     

Steric effect on construction of extended architectures of Ni(II) complexes directed by intermolecular C-H...F and C-H...O interactions

Five new Ni(II) complexes with pyridine carboxamide ligands have been synthesized and the crystal structures of three of the complexes were determined. Strong distortion effects of 6-methyl substitution were observed in the complexes with 6-methyl-substituted pyridyl bpb ligands. The C-H...F and C-H...O hydrogen bond interactions build extended architectures in the crystals studied. This result suggests that the steric effect of 6-methyl substitution plays an important role in the distortion of the structure, and the 6-methyl substitution can facilitate hydrogen bond interactions between methyl hydrogen atoms and O(carbonyl) or F atoms. Twelve Ni(II) complexes, including seven complexes reported previously, show reversible redox behavior, implying that the reduced Ni(I) state of each complex is stable in the time scale of CV measurement. The steric effect of R₁ substituent and the electronic effects of X₁ and X₂ groups were found to be the main factors contributing to the shift of the redox potential of the Ni(II) complexes     

Ruthenium dihydride complexes: NMR studies of intramolecular isomerization and fluxionality including the detection of minor isomers by parahydrogen-induced polarization

NMR studies reveal that complexes Ru(CO)(2)(H)(2)L(2) (L = PMe(3), PMe(2)Ph, and AsMe(2)Ph) can have three geometries, ccc, cct-L, and cct-CO, with equilibrium ratios that are highly dependent on the electronic properties of L; the cct-L form is favored, because the sigma-only hydride donor is located trans to CO rather than L. When L = PMe(3), the ccc form is only visible when p-H(2) is used to amplify its spectral features. In contrast, when L = AsMe(2)Ph, the ccc and cct-L forms are present in similar quantities and, hence, must have similar free energies; for this complex, however, the cct-CO isomer is also detectable. These complexes undergo a number of dynamic processes. For L(2) = dppe, an interchange of the hydride positions within the ccc form is shown to be accompanied by synchronized CO exchange and interchange of the two phosphorus atoms. This process is believed to involve the formation of a trigonal bipyramidal transition state containing an eta(2)-H(2) ligand; in view of the fact that k(HH)/k(DD) is 1.04 and the synchronized rotation when L(2) = dppe, this transition state must contain little H-H bonding character. Pathways leading to isomer interconversion are suggested to involve related structures containing eta(2)-H(2) ligands. The inverse kinetic isotope effect, k(HH)/k(DD) = 0.5, observed for the reductive elimination of dihydrogen from Ru(CO)(2)(H)(2)dppe suggests that substantial H-H bond formation occurs before the H(2) is actually released from the complex. Evidence for a substantial steric influence on the entropy of activation explains why Ru(CO)(2)(H)(2)dppe undergoes the most rapid hydride exchange. Our studies also indicate that the species [Ru(CO)(2)L(2)], involved in the addition of H(2) to form Ru(CO)(2)(H)(2)L(2), must have singlet electron configurations.     

Exploring carbohydrate-peptide interactions in the gas phase: structure and selectivity in complexes of pyranosides with N-acetylphenylalanine methylamide

The physical basis of carbohydrate-peptide interactions has been explored by probing the structures of a series of complexes generated in a solvent-free environment under molecular beam conditions. A combination of double-resonance IR-UV spectroscopy and quantum-chemical calculations has established the structures of complexes of the model, N-acetyl-L-phenylalanine methylamide, bound to the α and β anomers of methyl D-gluco- and D-galactopyranoside as guests. In all cases, the carbohydrates are bound through hydrogen bonding to the dipeptide chain, although with some differing patterns. The amino acid host "engages" with the most suitable pair of neighboring conjugate sites on each carbohydrate; the specific choice depends on the conformation of the peptide backbone and the configuration and conformation of the carbohydrate ligand. None of the structures is supported by "stacking" interactions with the aromatic ring, despite their common occurrence in bound carbohydrate-protein structures.