Transition metal ions coordination number

The D and A pathways proceed through intermediates of reduced and increased coordination numbers, respectively. The I mechanisms are characterized by the lack of an intermediate with a modified metal ion coordination number in the reaction. When bond breaking is more important than bond making the mechanism is Id the transition state has a reduced coordination number. In an Ia mechanism bond making is more important than bond breaking the transition state has an increased coordination number. 

For d-transition-metal ions, the number of water molecules in the primary coordination sphere (A-zone) is in most cases determined by the strength of orbital overlap between the metal ion and H2O molecules, crystal field stabilization effects, and cationic charge. Other species (e.g., alkaline earths, rare earths) interact with solvent molecules via ion-dipole forces with minimal orbital overlap conhibution to the bonding. Their solvation numbers are determined by a combination of coulombic attraction between cations and water molecules, steric fiictors, and van der Waals repulsion between the bound water molecules. The larger size and high charge of the lanthanides combine with the absence of directed valence effects to produce primary-sphere hydration numbers above eight for these metal ions. 

The aromatic shifts that are induced by 5.1c, 5.If and S.lg on the H-NMR spectrum of SDS, CTAB and Zn(DS)2 have been determined. Zn(DS)2 is used as a model system for Cu(DS)2, which is paramagnetic. The cjkcs and counterion binding for Cu(DS)2 and Zn(DS)2 are similar and it has been demonstrated in Chapter 2 that Zn(II) ions are also capable of coordinating to 5.1, albeit somewhat less efficiently than copper ions. Figure 5.7 shows the results of the shift measurements. For comparison purposes also the data for chalcone (5.4) have been added. This compound has almost no tendency to coordinate to transition-metal ions in aqueous solutions. From Figure 5.7 a number of conclusions can be drawn. (1) The shifts induced by 5.1c on the NMR signals of SDS and CTAB... 

Shannon and Prewitt base their effective ionic radii on the assumption that the ionic radius of (CN 6) is 140 pm and that of (CN 6) is 133 pm. Also taken into consideration is the coordination number (CN) and electronic spin state (HS and LS, high spin and low spin) of first-row transition metal ions. These radii are empirical and include effects of covalence in specific metal-oxygen or metal-fiuorine bonds. Older crystal ionic radii were based on the radius of (CN 6) equal to 119 pm these radii are 14-18 percent larger than the effective ionic radii. 

Cobalt exists in the +2 or +3 valence states for the majority of its compounds and complexes. A multitude of complexes of the cobalt(III) ion [22541-63-5] exist, but few stable simple salts are known (2). Werner s discovery and detailed studies of the cobalt(III) ammine complexes contributed gready to modem coordination chemistry and understanding of ligand exchange (3). Octahedral stereochemistries are the most common for the cobalt(II) ion [22541-53-3] as well as for cobalt(III). Cobalt(II) forms numerous simple compounds and complexes, most of which are octahedral or tetrahedral in nature cobalt(II) forms more tetrahedral complexes than other transition-metal ions. Because of the small stabiUty difference between octahedral and tetrahedral complexes of cobalt(II), both can be found in equiUbrium for a number of complexes. Typically, octahedral cobalt(II) salts and complexes are pink to brownish red most of the tetrahedral Co(II) species are blue (see Coordination compounds). 

Two possible reasons may be noted by which just the coordinatively insufficient ions of the low oxidation state are necessary to provide the catalytic activity in olefin polymerization. First, the formation of the transition metal-carbon bond in the case of one-component catalysts seems to be realized through the oxidative addition of olefin to the transition metal ion that should possess the ability for a concurrent increase of degree of oxidation and coordination number (177). Second, a strong enough interaction of the monomer with the propagation center resulting in monomer activation is possible by 7r-back-donation of electrons into the antibonding orbitals of olefin that may take place only with the participation of low-valency ions of the transition metal in the formation of intermediate 71-complexes. 

Coordination Numbers and Radii. In the transition metal ions, the interaction of the ligand orbitals with the d orbitals of the metal ions generally determines the coordination number and geometry of the oordination sphere about the metal. The... 

We are concerned with what happens to the (spectral) d electrons of a transition-metal ion surrounded by a group of ligands which, in the crystal-field model, may be represented by point negative charges. The results depend upon the number and spatial arrangements of these charges. For the moment, and because of the very common occurrence of octahedral coordination, we focus exclusively upon an octahedral array of point charges. 

There are a number of particular technical advantages associated with the formation of coloured metal complexes. Commonly, the transition metal complexes of a coloured organic ligand exhibit lightfastness which is significantly better than that of the free ligand. An explanation that has been offered for this effect is that coordination with a transition metal ion... 

The versatile binding modes of the Cu2+ ion with coordination number from four to six due to Jahn-Teller distortion is one of the important reasons for the diverse structures of the Cu-Ln amino acid complexes. In contrast, other transition metal ions prefer the octahedral mode. For the divalent ions Co2+, Ni2+, and Zn2+, only two distinct structures were observed one is a heptanuclear octahedral [LnM6] cluster compound, and the other is also heptanuclear but with a trigonal-prismatic structure. 

Much of what has been said so far in this chapter applies equally well to complexes of second- and third-row transition metals. However, there are some general differences that result from the fact that atoms and ions of the second- and third-row metals are larger in size than those of first-row metals. For example, because of their larger size (when in the same oxidation state as a first-row ion), ions of metals in the second and third rows form many more complexes in which they have a coordination number greater than 6. Whereas chromium usually has a coordination number of 6, molybdenum forms [Mo(CN)8]4 and other complexes in which the coordination number is 8. Other complexes of second- and third-row metals exhibit coordination numbers of 7 and 9. 

The second ligand type consists of a large group of cyclic compounds incorporating numbers of ether functions as donors. Structure (22) illustrates a typical example. Such crown polyethers usually show strong complexing ability towards alkali and alkaline earth ions but their tendency to coordinate to transition metal ions is less than for the above... 

These and many similar examples resulted in a highly successful general picture of transition-metal ions M coordinated by closed-shell ligands L (anionic or neutral) to form complex cluster ions [ML ]9 in solution. The characteristic coordination shell of each M corresponds to a specific number of sites, with idealized geometry that dictates the possible number of distinct [M(Li) (L2)m. .. ]q structural isomers. Each cluster ion is subject to equilibria with other cluster ions or dissociated ligands in solution,... 

If the coordination number of a given complex of a first row transition metal ion exceeds six there seems to be a general stabilization of the high-spin configuration. To our knowledge, there are no examples of Fe(II) crossover complexes with such high coordination numbers. 

Laser ablation of compounds of almost all elements in the periodic table will produce the bare ion M+. Laser ablation and other methods of producing bare metal ions have been discussed in Section II.C.5. The bare metal ion has a coordination number of 0 and for most elements these ions will aggressively seek molecules able to share or donate electrons. Thus most bare transition metal ions will increase their coordination number by reacting with any donor, this even includes the inert gas atoms such as Xe (96). 

There are many ligands in addition to water, for example Cl , NH3, CN , N02, and transition metal ions, in particular, form a large number of complex ions with different ligands. The number of ligands surrounding the central atom, or ion, is called the coordination number. The numerical value of the co-ordination number depends on a number of factors, but one important factor is the sizes of both the ligands and central atom, or ion. A number of complex ions are given below in Table 2 9. The shape of complex... 

Oxidations dependent on molecular oxygen are of fundamental importance to many chemical and biochemical processes (1.-6). A large number of these processes require the presence of some transition metal ion to "activate" the oxygen. The initial step in many of these reactions is the coordination of O2, and the... 

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