Electronic zinc compounds

IR and Raman spectroscopy have been commonly used and, for example, the effects of pressure on the Raman spectrum of a zinc compound with a N2C12 coordination sphere around the metal, have been investigated.28 IR spectroscopy has been utilized in studies of the hydration of zinc in aqueous solution and in the hydrated perchlorate salt.29 Gas phase chemistry of zinc complexes has been studied with some gas phase electron diffraction structures including amide and dithiocarbamate compounds.30-32... 

Square-planar zinc compounds predominate with these ligand types as would be predicted. This is in contrast to the prevalence of tetrahedral or distorted tetrahedral geometries for four-coordinate species that have been discussed thus far. Zinc porphyrin complexes are frequently used as building blocks in the formation of supramolecular structures. Zinc porphyrins can also act as electron donors and antenna in the formation of photoexcited states. Although the coordination of zinc to the porphyrin shows little variation, the properties of the zinc-coordinated compounds are extremely important and form the most extensively structurally characterized multidentate ligand class in the CSD. The examples presented here reflect only a fraction of these compounds but have been selected as recent and representative examples. Expanded ring porphyrins have also... 

The report of the first zinc compound with a Zn-Zn core elicited a number of critical comments on the structure and bonding of decamethyldizincocene, and the interpretation of the results.236,237 None of the authors of these commentaries questioned the data or their interpretation. Parkin, however, has pointed out that the formal oxidation state of +1 for zinc in this compound is merely due to the convention that metals are assigned an oxidation state of 0 when they form bonds with like atoms.237 If the conventional definition of valence, namely the capacity of atoms to form bonds to other atoms is used, then the zinc atoms in decamethyldizincocene are not monovalent, but divalent. The synthesis of a paramagnetic organozinc compound in which zinc uses only one of its two 4s electrons will remain an interesting challenge to many synthetic organometallic chemists. 

Cadmium is a member of Group 12 (Zn, Cd, Hg) of the Periodic Table, having a filled d shell of electrons 4valence state of +2. In rare instances the +1 oxidation state may be produced in the form of dimeric Cd2+2 species [59458-73-0], eg, as dark red melts of Cd° dissolved in molten cadmium halides or as diamagnetic yellow solids such as (Cd2)2+ (AlCl [79110-87-5] (2). The Cd + species is unstable in water or other donor solvents, immediately disproportionating to Cd2+ and Cd. In general, cadmium compounds exhibit properties similar to the corresponding zinc compounds. Compounds and properties are listed in Table 1. Cadmium(TT) [22537 48-0] tends to favor tetrahedral coordination in its compounds, particularly in solution as complexes, eg, tetraamminecadmium(II) [18373-05-2], Cd(NH3)2+4. However, solid-state cadmium-containing oxide or halide materials frequently exhibit octahedral coordination at the Cd2+ ion, eg, the rock-salt structure found for CdO. 

The (/-block elements tend to lose their valence s-electrons when they form compounds. Most of them can also lose a variable number of d-electrons and show variable valence. The only elements of the block that do not use their (/-electrons in compound formation are the members of Group 12 (zinc, cadmium, and mercury). The ability to exist in different oxidation states is responsible for many of the special properties of these elements and plays a role in the action of many vital biomolecules (Box 16.1). 

The filled 3d subshell is of little direct importance in zinc chemistry, in the sense that it remains intact in all zinc compounds and the 3d orbitals are not thought to take much part in bonding. It does, however, have a profound effect on the 4s electrons, which are rather poorly shielded from the nucleus by the 3d electrons. 

Many studies on the direct reaction of methyl chloride with silicon-copper contact mass and other metal promoters added to the silicon-copper contact mass have focused on the reaction mechanisms.7,8 The reaction rate and the selectivity for dimethyldichlorosilane in this direct synthesis are influenced by metal additives, known as promoters, in low concentration. Aluminum, antimony, arsenic, bismuth, mercury, phosphorus, phosphine compounds34 and their metal complexes,35,36 Zinc,37 39 tin38-40 etc. are known to have beneficial effects as promoters for dimethyldichlorosilane formation.7,8 Promoters are not themselves good catalysts for the direct reaction at temperatures < 350 °C,6,8 but require the presence of copper to be effective. When zinc metal or zinc compounds (0.03-0.75 wt%) were added to silicon-copper contact mass, the reaction rate was potentiated and the selectivity of dimethyldichlorosilane was enhanced further.34 These materials are described as structural promoters because they alter the surface enrichment of silicon, increase the electron density of the surface of the catalyst modify the crystal structure of the copper-silicon solid phase, and affect the absorption of methyl chloride on the catalyst surface and the activation energy for the formation of dimethyldichlorosilane.38,39 Cadmium is also a structural promoter for this reaction, but cadmium presents serious toxicity problems in industrial use on a large scale.41,42 Other metals such as arsenic, mercury, etc. are also restricted because of such toxicity problems. In the direct reaction of methyl chloride, tin in... 

Hybridization can also help explain the existence and structure of many inorganic molecular ions. Consider, for example, the zinc compounds shown here. At the top is shown the electron configuration of atomic zinc, and just below it, of the divalent zinc ion. Notice that this ion has no electrons at all in its 4-shell. In zinc chloride, shown in the third row, there are two equivalent chlorine atoms bonded to the zinc. The bonding orbitals are of sp character that is, they are hybrids of the 4s and one 4p orbital of the zinc atom. Since these orbitals are empty in the isolated zinc ion, the bonding electrons themselves are all contributed by the chlorine atoms, or rather, the chlor ide ions, for it is these that are the bonded species here. Each chloride ion possesses a complete octet of electrons, and two of these electrons occupy each sp bond orbital in the zinc chloride complex ion. This is an example of a coordinate covalent bond, in which the bonded atom contributes both of the electrons that make up the shared pair. 

Intermolecular Adduct Formation. The metal center in R2Cd compounds is noticeably less Lewis acidic than in the corresponding zinc compounds. Hence, R2Cd compounds form weaker, and fewer, adducts than do the R2Zn analogs. However, the Lewis acidity of the Cd center may be increased by incorporation of electron-withdrawing substituents. 

The zinc porphyrin is a Zn(II) species (two real Zn-N bonds and two dotted bonds) so it has 10 electrons. If we add eight for the four nitrogen ligands, we get 18 electrons. These compounds are stable and several substituted versions are sold by chemical companies. They will accept one extra ligand, for example, a pyridine, but this then pulls the zinc atom out of the plane of the porphyrin. 

Similarly, using phthalocyanine or porphyrin complexes of a range of transition elements, cobalt and iron again appear to be the best metal ions. Although the mechanisms of the reactions are not fully understood, it is believed that two-electron oxidation is again important and some correlation between oxygen yield and redox potential (M " /M " ) for the phthalocyanine complexes is observed. TTie anomalously low efficiency of zinc compounds compared with those of cobalt, which have similar first oxidation potentials, suggests that the second oxidation potentials are also important. ... 

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