Complex ions octahedral complexes

The aluminium ion, charge -I- 3. ionic radius 0.045 nm, found in aluminium trifluoride, undergoes a similar reaction when a soluble aluminium salt is placed in water at room temperature. Initially the aluminium ion is surrounded by six water molecules and the complex ion has the predicted octahedral symmetry (see Table 2.5 ) ... 

Silicon, germanium, tin and lead can make use of unfilled d orbitals to expand their covalency beyond four and each of these elements is able (but only with a few ligands) to increase its covalency to six. Hence silicon in oxidation state -f-4 forms the octahedral hexafluorosilicate complex ion [SiFg] (but not [SiCl] ). Tin and lead in oxidation state -1-4 form the hexahydroxo complex ions, hexahydroxostannate(IV). [Sn(OH) ] and hexahydroxoplum-bate(IV) respectively when excess alkali is added to an aqueous solution containing hydrated tin(IV) and lead(IV) ions. 

This is the most common and stable state of chromium in aqueous solution. The Cr ion, with 2d electrons, forms mainly octahedral complexes [CrX ], which are usually coloured, and are kweticallv inert, i.e. the rate of substitution of X by another hgand is very slow consequently a large number of such complexes have been isolated (see below, under chromium(III) chloride). 

Although the complex ion [MnClg] is unstable, salts such as K2[MnF6] (containing the octahedral hexafluoromanganate(IV) ion) are much more stable and can be crystallised from solution. 

Comparable with the chloride system, complex ions of the form M2 ThX3] (A =Br [44490-064], M = (CH3) N, (C2H3) N X = I [44490-18-8], M = (C2H3) N, (CH3)3C3H3N) are known where the metal center is octahedral. Additional information on thorium bromides and iodides can be found in the hterature (81). 

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... 

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). 

In general, octahedral complexes of transition-metal ions possessing 0, 1, or 2 electrons beyond the electronic configuration of the preceding noble gas, ie, i/, (P configurations, are labile. The (P systems are usually inert the relative lability of vanadium(II) may be charge and/or redox related. 

The most important low-spin octahedral complex of Mn is the dark-red cyano complex, [Mn(CN)6] , which is produced when air is bubbled through an aqueous solution of Mn and CN . [MnXs] (X = F, Cl) are also known the chloro ion, at least when combined with the cation [bipyH2] +, is notable as an example of a square pyramidal manganese complex. 

Aqueous solutions of salts with non-coordinating anions contain the pale-pink, [Mn(H20)6] +, ion which is one of a variety of high-spin octahedral complexes which have been... 

The 0s 02 " group has a formal similarity to the more familiar uranyl ion [U02] " and is present in a variety of octahedral complexes... 

Thc Crystal l-ield Siabili2ation Energy (CFSl ) is the additional stability which accrues to an ion in a complex, as compared to the free ion, because its d-orbitals are split In an octahedral complex a l2 electron increases the stability by 2/5Ao and an Cf, electron decreases it by 3/5Ao- In a tetrahedral complex the orbital splitting is reversed and an e electron therefore increases the stability by 3/5At whereas a t2 electron decreases it by 2/5Ai. 

In polymerizing these compounds, a reaction between a-TiCls and triethylaluminum produces a five coordinate titanium (111) complex arranged octahedrally. The catalyst surface has four Cl anions, an ethyl group, and a vacant catalytic site ( ) with the Ti(lll) ion in the center of the octahedron. A polymerized ligand, such as ethylene, occupies the vacant site ... 

We saw in Chapter 7 that octahedral geometry is characteristic of many molecules (e.g., SF6) in which a central atom is surrounded by six other atoms. (Remember, an octahedron has eight sides, which is irrelevant here it has six comers, which is important) All complex ions... 

Two or more species with different physical and chemical properties but the same formula are said to be isomers of one another. Complex ions can show many different kinds of isomerism, only one of which we will consider. Geometric isomers are ones that differ only in the spatial orientation of ligands around the central metal atom. Geometric isomerism is found in square planar and octahedral complexes. It cannot occur in tetrahedral complexes where all four positions are equivalent... 

As six ligands approach a central metal ion to form an octahedral complex, they change the energies of electrons in the d orbitals. The effect (Figure 15.10, p. 419) is to split the five d orbitals into two groups of different energy. 

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