Coordination numbers tetrahedral complexes

Coordination number Tetrahedral and square planar complexes exhibit higher labihty towards isotopic hgand exchange compared to the octahedral moieties. This is because of the avahabhity of a larger room for entry of the incoming ligands in case of four-coordinated complexes. 

Iron hahdes react with haHde salts to afford anionic haHde complexes. Because kon(III) is a hard acid, the complexes that it forms are most stable with F and decrease ki both coordination number and stabiHty with heavier haHdes. No stable F complexes are known. [FeF (H20)] is the predominant kon fluoride species ki aqueous solution. The [FeF ] ion can be prepared ki fused salts. Whereas six-coordinate [FeCy is known, four-coordinate complexes are favored for chloride. Salts of tetrahedral [FeCfy] can be isolated if large cations such as tetraphenfyarsonium or tetra alkylammonium are used. [FeBrJ is known but is thermally unstable and disproportionates to kon(II) and bromine. Complex anions of kon(II) hahdes are less common. [FeCfy] has been obtained from FeCfy by reaction with alkaH metal chlorides ki the melt or with tetraethyl ammonium chloride ki deoxygenated ethanol. 

Simple nickel salts form ammine and other coordination complexes (see Coordination compounds). The octahedral configuration, in which nickel has a coordination number (CN) of 6, is the most common stmctural form. The square-planar and tetrahedral configurations (11), iu which nickel has a coordination number of 4, are less common. Generally, the latter group tends to be reddish brown. The 5-coordinate square pyramid configuration is also quite common. These materials tend to be darker in color and mostiy green (12). 

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). 

The coordination number of Ni rarely exceeds 6 and its principal stereochemistries are octahedral and square planar (4-coordinalc) with rather fewer examples of trigonal bipyramidal (5), square pyramidal (5), and tetrahedral (4). Octahedral complexes of Ni arc obtained (often from aqueous solution by replacement of coordinated water) especially with neutral N-donor ligands such as NH3, en, bipy and phen, but also with NCS, N02 and the 0-donor dimethylsulfoxide. dmso (Me2SO). 

Geometry of four-coordinate complexes. Complexes in which the central metal has a coordination number of 4 may be tetrahedral or square planar. 

Fig. 22-3. A tetrahedral complex aluminum with coordination number 4.

In addition to the tetrahedral and octahedral complexes mentioned above, there are two other types commonly found—the square planar and the linear. In the square planar complexes, the central atom has four near neighbors at the corners of a square. The coordination number is 4, the same number as in the tetrahedral complexes. An example of a square planar complex is the complex nickel cyanide anion, Ni(CN)4-2. 

The next most common coordination number is 4. Two shapes are typically found for this coordination number. In a tetrahedral complex, the four ligands are found at the vertices of a tetrahedron, as in the tetrachlorocobaltate(ll) ion, [CoCl4]2 (2). An alternative arrangement, most notably for atoms and ions with ds electron configurations such as Pt2+ and Au +, is for the ligands to lie at the corners of a square, giving a square planar complex (3). 

Complexes with coordination number 6 tend to be octahedral those with coordination number 4 are either tetrahedral or square planar. Polydentate ligands can form chelates. 

We have argued that, once achieved, planar coordination in d systems is stable with respect to higher coordination number or tetrahedral distortion. The question arises then about what circumstances favour planarity in the first place. In particular, we enquire about the occurrence of tetrahedral verses square planar stereochemistry for d complexes. Why, for example, is the [Ni(CN)4] ion planar but [NiClJ tetrahedral ... 

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