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Coordinating Anions (coordinating + anion)
Kinds of Coordinating Anions Selected AbstractsCan Weakly Coordinating Anions Stabilize Mercury in Its Oxidation State +IV?CHEMISTRY - A EUROPEAN JOURNAL, Issue 9 2005Sebastian Riedel Dipl.-Chem. Abstract While the thermochemical stability of gas-phase HgF4 against F2 elimination was predicted by accurate quantum chemical calculations more than a decade ago, experimental verification of "truly transition-metal" mercury(IV) chemistry is still lacking. This work uses detailed density functional calculations to explore alternative species that might provide access to condensed-phase HgIV chemistry. The structures and thermochemical stabilities of complexes HgIVX4 and HgIVF2X2 (X,=AlF4,, Al2F7,, AsF6,, SbF6,, As2F11,, Sb2F11,, OSeF5,, OTeF5,) have been assessed and are compared with each other, with smaller gas-phase HgX4 complexes, and with known related noble gas compounds. Most species eliminate F2 exothermically, with energies ranging from only about ,60 kJ,mol,1 to appreciable ,180 kJ,mol,1. The lower stability of these species compared to gas-phase HgF4 is due to relatively high coordination numbers of six in the resulting HgII complexes that stabilize the elimination products. Complexes with AsF6 ligands appear more promising than their SbF6 analogues, due to differential aggregation effects in the HgII and HgIV states. HgF2X2 complexes with X,=OSeF5, or OTeF5, exhibit endothermic fluorine elimination and relatively weak interactions in the HgII products. However, elimination of the peroxidic (OEF5)2 coupling products of these ligands provides an alternative exothermic elimination pathway with energies between ,120 and ,130 kJ,mol,1. While all of the complexes investigated here thus have one exothermic decomposition channel, there is indirect evidence that the reactions should exhibit nonnegligible activation barriers. A number of possible synthetic pathways towards the most interesting condensed-phase HgIV target complexes are proposed. [source] Receptor versus Counterion: Capability of N,N, -Bis(2-aminobenzyl)-diazacrowns for Giving Endo- and/or Exocyclic Coordination of ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007Lea Vaiana Abstract The structure of ZnII complexes with receptors L1 and L2[L1 = N,N, -bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and L2 = N,N, -bis(2-aminobenzyl)-4,13-diaza-18-crown-6] was studied both in the solid state and in acetonitrile solution. Both receptors form mononuclear ZnII complexes in this solvent, while no evidence for the formation of dinuclear complexes was obtained. This is in contrast with previous investigations that demonstrated the formation of dinuclear complexes of L2 with first-row transition metals such as NiII, CoII and CuII. Compounds of formula [Zn(L1)](ClO4)2 (1), [Zn(L1)](NO3)2·2CH3CN (2), [Zn(L2)](ClO4)2 (3) and [Zn(L2)(NO3)2] (4) were isolated and structurally characterised by X-ray diffraction analyses. L1 forms seven-coordinate ZnII complexes in the presence of both nitrate and perchlorate anions, as a consequence of the good fit between the macrocyclic cavity and the ionic radius of the metal ion. The ZnII ion is deeply buried into the receptor cavity and the anions are forced to remain out of the metal coordination sphere. The cation [Zn(L1)]2+ present in 1 and 2 is one of the very few examples of seven-coordinate Zn complexes. Receptor L2 provides a very rare example of a macrocyclic receptor allowing endocyclic and exocyclic coordination on the same guest cation, depending on the nature of the anion present. Thus, in 3 the ZnII ion is endocyclically coordinated, placed inside the crown hole coordinated to four donor atoms of the ligand in a distorted tetrahedral environment, whereas in 4, the presence of a strongly coordinating anion such as nitrate results in an exocyclic coordination of ZnII, which is directly bound only to the two primarily amine groups of L2 and two nitrate ligands. Spectrophotometric titrations of [Zn(L2)]2+ with tetrabutylammonium nitrate in acetonitrile solution demonstrate the stepwise formation of 1:1 and 1:2 adducts with this anion in acetonitrile solution. The [Zn(L1)]2+, [Zn(L2)]2+ and [Zn(L2)(NO3)2] systems were characterised by means of DFT calculations (B3LYP model). The calculated geometries show an excellent agreement with the experimental structures obtained from X-ray diffraction analyses. Calculated binding energies of the macrocyclic ligands to ZnII are also consistent with the experimental data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] [1-Me-1- closo -SnB11H11], as a potential weakly coordinating anion: Synthesis of Rh(PPh3)2(1-Me- closo -SnB11H11) and comparisons with Rh(PR3)2 (1-H- closo -CB11 H11)HETEROATOM CHEMISTRY, Issue 3 2006Eduardo Molinos The closo -stannaborane salt [Rh(PPh3)2 -(nbd)][1-Me-1- closo -SnB11H11] reacts with H2 in CH2 Cl2 solution to afford the contact ion-pair Rh(PPh3)2(1-Me- closo -SnB11H11), which has been characterized in solution and the solid state by X-ray diffraction. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:174,180, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20218 [source] Pyrazolate-Based Dinucleating Ligands in L2M2 Scaffolds: Effects of Bulky Substituents and Coligands on Structures and M···H,C InteractionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2004Jens C. Röder Abstract A series of nickel(II) and palladium(II) complexes [L2M2]2+ have been prepared and structurally characterized, where L is a pyrazolate ligand with bulky 2,6-dimethyl- or 2,6-di(isopropyl)anilinomethyl side arms. Coordinating counter anions such as chloride can bind to axial sites of the dinickel species in a solvent-dependent process, giving rise to five-coordinate high-spin metal ions. In the case of weakly coordinating anions, the metal ions are found in roughly square-planar environments, and the structures are governed by the tendency of the bulky aryl groups to avoid each other, which forces the methyl or isopropyl substituents in the aryl 2- and 6-positions to approach the metal ions from the axial directions. This leads to drastic low-field shifts of the respective 1H NMR signals, e.g. , = 7.86 ppm for the isopropyl ,CH which comes in close proximity to the low-spin nickel(II) center. The relevance of such low-field NMR resonances of protons close to the axial sites of d8 metal ions for possible three-center four-electron M···H,C hydrogen bonds involving the filled d orbital of the metal ion is discussed. In the present case, attractive M···H interactions are assumed to be of no major significance. This was corroborated by the structure of a further [L2Ni2]2+ type complex where the anilinomethyl side arms bear only a single 2-isopropyl group, which was found rotated away from the metal. Additional spectroscopic and electrochemical properties of the various complexes are reported. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Alkyne Hydroarylations with Chelating Dicarbene Palladium(II) Complex Catalysts: Improved and Unexpected Reactivity Patterns Disclosed Upon Additive Screening,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 19 2009Andrea Biffis Abstract Palladium(II) complexes with a ligand set made from a chelating N-heterocyclic dicarbene ligand and two weakly coordinating anions (generally introduced in situ upon addition of 2 equiv. of a suitable silver salt) were found to be very active and selective catalysts for the room-temperature hydroarylation of alkynes at low catalyst loading (0.1 mol-%). Moreover, the screening of various strong acids as reaction promoters revealed that both the strength of the acid and the coordinating ability of its conjugated base influence the catalytic performance. Most remarkably, the use of HBF4 together with a dicarbene Pd complex catalyst provides a dramatic change in the selectivity of the reaction, with the prevalent formation of a product stemming from the insertion of two molecules of alkyne into the aromatic C,H bond. The results presented herein highlight the fact that the dicarbene ligand, apart from stabilising the catalyst, is also able to enhance catalytic activity and, most notably, to steer the reaction selectivity towards novel products. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Triazolate Counter Ions in AuI Complexes: Catalysts with Improved Thermal StabilityCHEMCATCHEM, Issue 2 2010Stephen Counter revolution: Most homogeneous gold-catalyzed transformations employ gold(I) complexes with weakly coordinating anions, which, their remarkable activity notwithstanding, lack stability at higher temperatures. Shi et,al. have described the synthesis of simple phosphine-based gold(I) complexes with triazolates as counter ions. The compounds are highly thermostable and good catalysts for intermolecular hydroaminations. [source] Towards a Molecular Understanding of Cation,Anion Interactions,Probing the Electronic Structure of Imidazolium Ionic Liquids by NMR Spectroscopy, X-ray Photoelectron Spectroscopy and Theoretical CalculationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 30 2010Till Cremer Abstract Ten [C8C1Im]+ (1-methyl-3-octylimidazolium)-based ionic liquids with anions Cl,, Br,, I,, [NO3],, [BF4],, [TfO],, [PF6],, [Tf2N],, [Pf2N],, and [FAP], (TfO=trifluoromethylsulfonate, Tf2N=bis(trifluoromethylsulfonyl)imide, Pf2N=bis(pentafluoroethylsulfonyl)imide, FAP=tris(pentafluoroethyl)trifluorophosphate) and two [C8C1C1Im]+ (1,2-dimethyl-3-octylimidazolium)-based ionic liquids with anions Br, and [Tf2N], were investigated by using X-ray photoelectron spectroscopy (XPS), NMR spectroscopy and theoretical calculations. While 1H,NMR spectroscopy is found to probe very specifically the strongest hydrogen-bond interaction between the hydrogen attached to the C2 position and the anion, a comparative XPS study provides first direct experimental evidence for cation,anion charge-transfer phenomena in ionic liquids as a function of the ionic liquid's anion. These charge-transfer effects are found to be surprisingly similar for [C8C1Im]+ and [C8C1C1Im]+ salts of the same anion, which in combination with theoretical calculations leads to the conclusion that hydrogen bonding and charge transfer occur independently from each other, but are both more pronounced for small and more strongly coordinating anions, and are greatly reduced in the case of large and weakly coordinating anions. [source] Self-Assembly of Calix[6]arene,Diazapyrenium Pseudorotaxanes: Interplay of Molecular Recognition and Ion-Pairing EffectsCHEMISTRY - A EUROPEAN JOURNAL, Issue 11 2010Monica Semeraro Abstract The calix[6]arene wheel CX forms pseudorotaxane species with the diazapyrenium-based axle 1,2PF6 in CH2Cl2 solution. The macrocyclic component is a heteroditopic receptor, which can complex the electron-acceptor moiety of the axle inside its cavity and the counterions with the ureidic groups on the upper rim. The self-assembled supramolecular species is a complex structure, which involves three components,the wheel, the axle and its counterions,that can mutually interact and affect. The stoichiometry of the resulting supramolecular complex depends on the nature and concentration of the counterions. Namely, it is observed that in dilute solution and with low-coordinating anions the axle takes two wheels, whereas with highly coordinating anions or in concentrated solutions the complex has a 1:1 stoichiometry. [source] Cu[Al(ORF)4] Starting Materials and their Application in the Preparation of [Cu(Sn)]+ (n=12, 8) ComplexesCHEMISTRY - A EUROPEAN JOURNAL, Issue 27 2009Gustavo Santiso-Quiñones Dr. Abstract Naked copper,? A newly developed simple two-step route to weakly coordinated CuI starting materials that were used to prepare novel copper,cyclosulfur adducts, including the first M+,S12 complex (see figure, RF= C(CF3)3, C(CH3)(CF3)2, or CH(CF3)2). Reactions with the [Al{OC(CF3)3}4], counterion mimic gas-phase chemistry inside a mass spectrometer (to form [Cu(S12)]+). An effective route to stable, almost-"naked" CuI salts of weakly coordinating anions (WCAs) of the type [Al(ORF)4], has been developed. Born,Fajans,Haber cycles and theoretical calculations suggest that this methodology is useful for the generation of CuI salts regardless of the larger WCA used. The first homoleptic CuI,arene complex [Cu(1,2-F2C6H4)2]+[Al{OC(CF3)3}4], (1), the first CuI,methylenechloride complex [Cu(CH2Cl2)Al{OC(CH3)(CF3)2}4] (2), and the donor-free dimer [CuAl{OCH(CF3)2}4]2 (3) were synthesized in quantitative yields by sonicating Li[Al(ORF)4] (RF=C(CF3)3, C(CH3)(CF3)2, or CH(CF3)2), AgF, and a three-fold excess of CuI in 1,2-F2C6H4 (1) or CH2Cl2 (2, 3). Substances 1,3 are good starting materials for further CuI chemistry, and the reaction of 1,3 with the weak Lewis base cyclooctasulfur gave the first CuI,sulfur complexes of type [Cu(S12)(S8)]+[Al{OC(CF3)3}4], (4), [Cu(CH2Cl2)(S12)]+[Al{OC(CF3)3}4], (5), [A1Cu(1,5-,1,,1 -S8)CuA1] (6; A1=[Al{OC(CH3)(CF3)2}4],), and a CuI,S8 1D coordination polymer with [Cu2(S8)2A22] (7; A2=[Al{OCH(CF3)2}4],), as a monomeric repeat unit. Complexes 4 and 5 are the first example of any metal coordinated to cyclo-S12 and 4 is the first example of a complex having an element in two allotropic modifications as a ligand. [source] | ||||||||||