Complex ions bonding

The ability to form hydrogen bonds explains the formation of complex ions such as HFJ and HjFj when a fluoride salt, for example potassium fluoride, is dissolved in aqueous hydrofluoric acid ... 

The bond dissociation energy of the hydrogen-fluorine bond in HF is so great that the above equilibrium lies to the left and hydrogen fluoride is a weak acid in dilute aqueous solution. In more concentrated solution, however, a second equilibrium reaction becomes important with the fluoride ion forming the complex ion HFJ. The relevant equilibria are ... 

The chemistry of Cr(III) in aqueous solution is coordination chemistry (see Coordination compounds). It is dominated by the formation of kineticaHy inert, octahedral complexes. The bonding can be described by Ss]] hybridization, and HteraHy thousands of complexes have been prepared. The kinetic inertness results from the electronic configuration of the Cr ion (41). This type of orbital charge distribution makes ligand displacement and... 

Complex ions used for electroplating are anions. The cathode tends to repel them, and their transport is entirely by diffusion. Conversely, the field near the cathode assists cation transport. Complex cyanides deserve some elaboration in view of their commercial importance. It is improbable that those used are covalent co-ordination compounds, and the covalent bond breaks too slowly to accommodate the speed of electrode reactions. The electronic structure of the cyanide ion is ... 

The Cu(NH3)42+ ion is commonly referred to as a complex ion, a charged species in which a central metal cation is bonded to molecules and/or anions referred to collectively as ligands. The number of atoms bonded to the central metal cation is referred to as its coordination number. In the Cu(NH3)42+ complex ion—... 

When a complex ion is formed from a simple cation, the electron pairs required for bond formation come solely from the ligands. Reactions such as these, in which one species donates an electron pair to another, are referred to as Lewis acid-base reactions. In particular—... 

Figure 15.2 (p. 412) shows the structure of the chelates formed by copper(II) with these ligands. Notice that in both of these complex ions, the coordination number of copper(II) is 4. The central cation is bonded to four atoms, two from each ligand. 

Complex ions in which the central metal forms only two bonds to ligands are linear that is, the two bonds are directed at a 180° angle. The structures of CuCl2, Ag(NH3)2+, and Au(CN)2 may be represented as... 

Until about 20 years ago, the valence bond model discussed in Chapter 7 was widely used to explain electronic structure and bonding in complex ions. It assumed that lone pairs of electrons were contributed by ligands to form covalent bonds with metal atoms. This model had two major deficiencies. It could not easily explain the magnetic properties of complex ions. 

Central metal cation Monatomic metal cation to which all the ligands are bonded in a complex ion, 409 Cerium (IV) oxide, 147 Chadwick, James, 517 Chalcocite, 539... 

Coordination number The number of bonds from the central metal to the ligands in a complex ion, 409,412t four-coordinate metal complex, 413 six-coordinate metal complex, 413-414 Copper, 412 blister, 539... 

Ligand A molecule or anion bonded to the central metal in a complex ion, 409 characterization, 411-412 nomenclature, 648-649 Light, 159q absorption, 421 particle nature of, 135-136 wave nature of, 133-135 Limiting reactant The least abundant... 

Sharing of an oxygen atom by two central atoms in compounds with chain-type structures weakens the binary Nb=0 bond compared to the corresponding bond in pure isolated ions such as NbOF52 This phenomenon affects the vibration spectra and increases wave numbers of NbO vibrations in the case of isolated oxyfluoride complex ions. Table 31 displays IR absorption spectra of some chain- type compounds. Raman spectra are discussed in [212],... 

The formulated principals correlating crystal structure features with the X Nb(Ta) ratio do not take into account the impact of the second cation. Nevertheless, substitution of a second cation in compounds of similar types can change the character of the bonds within complex ions. Specifically, the decrease in the ionic radius of the second (outer-sphere) cation leads not only to a decrease in its coordination number but also to a decrease in the ionic bond component of the complex [277]. 

The spectra of the initial saturated solution, with a F Nb of approximately 6, are of particular interest because of the presence of a weak band at about 900-930 cm 1. This band can be attributed to NbO bonds in oxyfluoride complexes. Even small additions of HF lead to the disappearance of the above effect. This can be explained based on a complex solvatation model. In solutions with a F Nb ratio of about 6, hexafluoroniobate complex, NbF6, initiates the formation of HF that interacts with complex ions as a solvate. This process is called autosolvatation and is represented by two interactions. The first is a hydrolysis process that leads to the formation of HF ... 

Molten salts are characterized by the formation of discrete complex ions that are subjected to coordination phenomenon. Such complex ions have specific compositions that are related to the rearrangement of their electronic configuration and to the formation of partially covalent bonds. The life time of the coordinated ions is longer than the contact period of the individual ions [293]. 

A slight but systematic decrease in the wave number of the complexes bond vibrations, observed when moving from sodium to cesium, corresponds to the increase in the covalency of the inner-sphere bonds. Taking into account that the ionic radii of rubidium and cesium are greater than that of fluorine, it can be assumed that the covalent bond share results not only from the polarization of the complex ion but from that of the outer-sphere cation as well. This mechanism could explain the main differences between fluoride ions and oxides. For instance, melts of alkali metal nitrates display a similar influence of the alkali metal on the vibration frequency, but covalent interactions are affected mostly by the polarization of nitrate ions in the field of the outer-sphere alkali metal cations [359]. 

Adding potassium hydroxide, KOH, to a melt containing KF and a 0.1 mol fraction of K2TaF7 leads to the appearance of an additional band at 900 cm 1, as shown in Fig. 79 [342]. This band corresponds to TaO bond vibrations in TaOF63 complex ions. Interpretation of IR spectra obtained from more concentrated melts is less clear (Fig. 80). The observed absorption in the range of 900-700 cm 1 indicates the formation of oxyfluoride polyanions with oxygen bridges. ..OTaO. The appearance of a fine band structure could be related to very low concentrations of some isolated components. These isolated conditions prevent resonance interaction between components and thus also prevent expansion of the bands by a mechanism of resonance [362]. 

Combining volumes, law of, 26, 236 Combustion, heat of hydrogen, 40 Complex ions, 392 amphoteric, 396 bonding in, 395 formation, 413 geometry of. 393 in nature, 396 isomers, 394 linear, 395 octahedral, 393 significance of, 395 square planar, 395 tetrahedral, 394 weak acids, 396 Compound, 28 bonding in, 306 Concentration and equilibrium, 148 and E zero s, 213 and Le Chatelier s Principle, 149 effect on reaction rate, 126, 128 molar, 72... 

The thermodynamic analysis of the selectivity of ion exchange with the participation of ions of quaternary ammonium bases [56--58] has shown that an increase in bonding selectivity, when metal ions are replaced by organic ions, which is usually accompanied by an increase in entropy of the system (Table 5). It follows from Table 5 that a drastic increase in bonding selectivity upon passing to a triethylbenzylammonium counterion (the most complex ion) is due to a considerable increase in the entropy of the system. 

The sorption selectivity for more complex ions (e.g., ions of antibiotics) in competition with small ions increases to a still greater extent [59]. Particularly high constants for selective bonding (up to some hundreds and thousand) have... 

Figure 4.17 A qualitative molecular orbital scheme for a cr-bonded complex ion [AuL2]+. (Reprinted with permission from Inorg. Chem., 1982, 21, 2946. Copyright (1982) American...

The proton is not the only entity that can dissociate from a substrate or bond to it. We can enumerate other interactions, such as metal-ligand complexation, ion-pair formation, charge-transfer complex formation, etc. For the sake of brevity, we treat all of these as... 

In other cases, discussed below, the lowest electron-pair-bond structure and the lowest ionic-bond structure do not have the same multiplicity, so that (when the interaction of electron spin and orbital motion is neglected) these two states cannot be combined, and a knowledge of the multiplicity of the normal state of the molecule or complex ion permits a definite statement as to the bond type to be made. 

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