Metal coordination number

Oxidation state Electronic configuration Coordination number Metal atom geometry Example CAS Registry Number... 

Fourier transformation of Cu EXAFS data gathered on the Cu(MPG) complex reveals two separate peaks representing shells at distances of 1.9 and 2.3 A. When tested for Ns (coordination number), metal-ligand distance (R as), and Debye-Waller parameter difference (Aa2as) followed by comparison to known model compounds, results show that the presence of both a Cu-(N, O) and Cu-S shell is necessary to obtain an adequate fit to the EXAFS data. Therefore it was concluded that a Cu-S bond is present in the compound. 

Compound Ref. Average M—C Bond Length (A) Formal Metal ) Ion Coordination Number Metal lonict) Radius (A) Efiective COT Ionic Radius (A)... 

It is also possible to use extended X-ray absorption fine-structure (EXAFS) spectroscopy to deduce particle sizes, and this method has been used, along with hydrogen chemisorption, to study Rh, Pt, and Ir supported on Si02 and A1203 (147, 150). The average coordination number of the metal atoms is calculated from the EXAFS results. A model implemented by computer is then used to estimate the particle size from the coordination number. Metal support interaction can be included in the model. 

Metallomesogens Based on High Coordination Number Metal Centres... 

For many years, the only examples of formally six-coordinate metal complexes forming lamellar mesophases were derivatives of ferrocene, while the vast majority of calamitic metallomesogens were based essentially on two- and four-coordinate complexes of metals from groups 8 and 10. Novel metallomesogens based on high coordination number metal centres were recently reported to show nematic and lamellar mesophases. 

An electrophilic character is also found for low-coordination number metal atoms at kinks and steps in metal surfaces.These sites are also known to be much more active for alkane reactions than the flat metal surfaces. 

The driving force behind this is again based on coordination numbers. Metal atoms in the bulk are 12-coordinate, whereas they are 8 for the surfoce atoms in 23.12. Thus, the surfece atoms are coordinatively unsaturated and this electron deficiency can be partially ameliorated by forming stronger (shorter) bonds to metals in the second layer. A frequent occurrence in (110) surfeces is that every other row along the [I To] direction is missing. A side view of this surfoce reconstruction is given in 23.13. There are also well-documented cases where adsorbates can drive the structure back to a flat surfece. The electronic mechanism for these distortions is complicated and will not be repeated here [6], Surfoce reconstructions in semiconductors are examined in Section 23.5. 

The melting and boiling points of the aluminium halides, in contrast to the boron compounds, are irregular. It might reasonably be expected that aluminium, being a more metallic element than boron, would form an ionic fluoride and indeed the fact that it remains solid until 1564 K. when it sublimes, would tend to confirm this, although it should not be concluded that the fluoride is, therefore, wholly ionic. The crystal structure is such that each aluminium has a coordination number of six, being surrounded by six fluoride ions. 

The change in colour when one ligand is replaced by another can be used to determine the coordination number thus if the colour change is measured in a colorimeter as the new ligand is added, the intensity of new colour reaches a maximum When the metal/ligand ratio is that in the new complex. 

It can be readily confirmed thaf by decreases as the number of bonds N increases and/or llieir length (r ) decreases. This relationship between the bond strength and the number of neighbours provides a useful way to rationalise the structure of solids. Thus the high coordination of metals suggests that it is more effective for them to form more bonds, even though each individual bond is weakened as a consequence. Materials such as silicon achieve the balance for an infermediate number of neighbours and molecular solids have the smallest atomic coordination numbers. 

PM3/TM is an extension of the PM3 method to transition metals. Unlike the parameterization of PM3 for organics, PM3/TM has been parameterized only to reproduce geometries. This does, of course, require a reasonable description of energies, but the other criteria used for PM3 parameterization, such as dipole moments, are not included in the PM3/TM parameterization. PM3/TM tends to exhibit a dichotomy. It will compute reasonable geometries for some compounds and completely unreasonable geometries for other compounds. It seems to favor one coordination number or hybridization for some metals. 

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. 

Gold Compounds. The chemistry of nonmetallic gold is predominandy that of Au(I) and Au(III) compounds and complexes. In the former, coordination number two and linear stereochemistry are most common. The majority of known Au(III) compounds are four coordinate and have square planar configurations. In both of these common oxidation states, gold preferably bonds to large polarizable ligands and, therefore, is termed a class b metal or soft acid. 

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. 

Phosphorus compounds exhibit an enormous variety of chemical and physical properties as a result of the wide range ia the oxidation states and coordination numbers for the phosphoms atom. The most commonly encountered phosphoms compounds are the oxide, haUde, sulfide, hydride, nitrogen, metal, and organic derivatives, all of which are of iadustrial importance. The hahde, hydride, and metal derivatives, and to a lesser extent the oxides and sulfides, are reactive iatermediates for forming phosphoms bonds with other elements. Phosphoms-containing compounds represented about 6—7% of the compound hstiugs ia Chemical Abstracts as of 1993 (1). 

Stmctures are highly varied among the transition metals. The titanium atom in titanium tetraethoxide has the coordination number 6 (Fig. 1). The corresponding zirconium compound, with coordination number 8, has a different stmcture (Fig. 2). Metal alkoxides are colored when the corresponding metal ions are colored, otherwise they are not. 

The chemistry of Th(IV) has expanded greatly since the mid-1980s (14,28,29). Being a hard metal ion, Th(IV) has the greatest affinity for hard donors such as N, O, and light haUdes such as F and CF. Coordination complexes that are common for the t7-block elements have been studied for thorium. These complexes exhibit coordination numbers ranging from 4 to 11. 

By far the most important metal containing dyes are derived from OjO-dUiydroxyazo stmctures in which one of the two azo nitrogen atoms and the two hydroxyl oxygen atoms are involved in bonding with the metal ion. Thus these dyes serve as terdentate ligands. In the case of metal ions with a coordination number of four, eg, Cu(H), the fourth position is usuaUy occupied by a solvent molecule (47). 

A hydroxyl group is situated ortho to a carboxyl group which as a bidentate ligand is terminally metallized on the fiber when aftertreated with dichromate. An example is Alizarine Yellow GG [584-42-9] (50) (Cl Mordant Yellow 1 Cl 14025). Cr(III) has a coordination number of six, and therefore normally two dye molecules of the sahcyhc type are chelated to the metal ion. 

Bismuthides. Many intermetaUic compounds of bismuth with alkafl metals and alkaline earth metals have the expected formulas M Bi and M Bi, respectively. These compounds ate not saltlike but have high coordination numbers, interatomic distances similar to those found in metals, and metallic electrical conductivities. They dissolve to some extent in molten salts (eg, NaCl—Nal) to form solutions that have been interpreted from cryoscopic data as containing some Bi . Both the alkafl and alkaline earth metals form another series of alloylike bismuth compounds that become superconducting at low temperatures (Table 1). The MBi compounds are particularly noteworthy as having extremely short bond distances between the alkafl metal atoms. 

Mononuclear Carbonyls. The lowest coordination number adopted by an isolable metal carbonyl is four. The only representative of this class is nickel carbonyl [13463-39-3] the first metal carbonyl isolated (15). The molecule possesses tetrahedral geometry as shown in stmcture (1). A few transient four-coordinate carbonyls, such as Fe(CO)4, have also been detected (16). 

Chromium (II) also forms sulfides and oxides. Chromium (II) oxide [12018-00-7], CrO, has two forms a black pyrophoric powder produced from the action of nitric acid on chromium amalgam, and a hexagonal brown-red crystal made from reduction of Cr202 by hydrogen ia molten sodium fluoride (32). Chromium (II) sulfide [12018-06-3], CrS, can be prepared upon heating equimolar quantities of pure Cr metal and pure S ia a small, evacuated, sealed quartz tube at 1000°C for at least 24 hours. The reaction is not quantitative (33). The sulfide has a coordination number of six and displays a distorted octahedral geometry (34). 

The colors obtained depend primarily on the oxidation state and coordination number of the coloring ion (3). Table 1 Hsts the solution colors of several ions in glass. AH of these ions are transition metals some rare-earth ions show similar effects. The electronic transitions within the partially filled d andy shells of these ions are of such frequency that they fall in that narrow band of frequencies from 400 to 700 nm, which constitutes the visible spectmm (4). Hence, they are suitable for producing color (qv). 

---