Diamagnetism and

The two primary causes of shielding by electrons are diamagnetism and temperature-independent paramagnetism (TIP). Diamagnetism arises from the slight unpairing of electron orbits under the influence of the magnetic field. This always occurs so as to oppose the field and was first analysed by Lamb [7]. A simplified version of his fomuila. 

The red precipitates of AgF are diamagnetic and isostmctural with AuF. Silver trifluoride is a powerful oxidizing agent and thermodynamically unstable. 

Silver(III) Compounds. No simple silver(Ill) compounds exist. When mixtures of potassium or cesium haUdes are heated with silver hahdes ia a stream of fluorine gas, yellow KAgF [23739-18-6] or CsAgF [53585-89-0] respectively, are obtained. These compounds are diamagnetic and extremely sensitive to moisture (21). When Ag2S04 is treated with aqueous potassium persulfate ia the presence of ethylenedibiguanidinium sulfate, the relatively stable Ag(Ill)-ethylenebiguanide complex is formed. 

Tungsten tetrachloride [13470-14-9], WCl, is obtained as a coarse, crystalline, deHquescent soHd that decomposes upon heating. It is diamagnetic and maybe prepared by the thermal-gradient reduction of WCl with aluminum (10). 

Vanadium, a typical transition element, displays weU-cliaractetized valence states of 2—5 in solid compounds and in solutions. Valence states of —1 and 0 may occur in solid compounds, eg, the carbonyl and certain complexes. In oxidation state 5, vanadium is diamagnetic and forms colorless, pale yeUow, or red compounds. In lower oxidation states, the presence of one or more 3d electrons, usually unpaired, results in paramagnetic and colored compounds. All compounds of vanadium having unpaired electrons are colored, but because the absorption spectra may be complex, a specific color does not necessarily correspond to a particular oxidation state. As an illustration, vanadium(IV) oxy salts are generally blue, whereas vanadium(IV) chloride is deep red. Differences over the valence range of 2—5 are shown in Table 2. The stmcture of vanadium compounds has been discussed (6,7). 

The copper(I) ion, electronic stmcture [Ar]3t/ , is diamagnetic and colorless. Certain compounds such as cuprous oxide [1317-39-1] or cuprous sulfide [22205-45 ] are iatensely colored, however, because of metal-to-ligand charge-transfer bands. Copper(I) is isoelectronic with ziac(II) and has similar stereochemistry. The preferred configuration is tetrahedral. Liaear and trigonal planar stmctures are not uncommon, ia part because the stereochemistry about the metal is determined by steric as well as electronic requirements of the ligands (see Coordination compounds). 

The difficulty of assigning a formal oxidation state is more acutely seen in the case of 5-coordinate NO adducts of the type [Co(NO)(salen)]. These are effectively diamagnetic and so have no unpaired electrons. They may therefore be formulated either as Co -NO or Co -NO+. The infrared absorptions ascribed to the N-O stretch lie in the range 1624-1724 cm which is at the lower end of the range said to be characteristic of NO+. But, as in all such cases which are really concerned with the differing polarities of covalent bonds, such formalism should not be taken literally. 

Planar-octahedral equilibria. Dissolution of planar Ni compounds in coordinating solvents such as water or pyridine frequently leads to the formation of octahedral complexes by the coordination of 2 solvent molecules. This can, on occasions, lead to solutions in which the Ni has an intermediate value of jie indicating the presence of comparable amounts of planar and octahedral molecules varying with temperature and concentration more commonly the conversion is complete and octahedral solvates can be crystallized out. Well-known examples of this behaviour are provided by the complexes [Ni(L-L)2X2] (L-L = substituted ethylenediamine, X = variety of anions) generally known by the name of their discoverer I. Lifschitz. Some of these Lifschitz salts are yellow, diamagnetic and planar, [Ni(L-L)2]X2, others are blue, paramagnetic, and octahedral, [Ni(L-L)2X2] or... 

Complexes of and The effect of complexation on the splitting of d orbitals is much greater in the case of second- and third-than for first-row transition elements, and the associated effects already noted for Ni are even more marked for Pd and Pi as a result, their complexes are, with rare exceptions, diamagnetic and the vast majority are planar also. Not many complexes are formed with O-donor ligands but, of the few that arc, [M(H20)4] ions, and the polymeric anhydrous acetates [Pd(02CMe)2l3 and [Pt(02CMc)2]4 (Fig. 27.10), are the most... 

All M cations of this triad are diamagnetic and, unless coordinated to easily polarized ligands, colourless too. In aqueous solution the Cu ion is very unstable with respect to disproportionation (2Cu v - Cu + Cu(s)) largely because of the high heat of hydration of the divalent ion as already mentioned. At 25°C, K (= [Cu ][Cu ]-2) is large, (5.38 0.37) x 10 1mol , and standard reduction potentials have been calculated to be ... 

Fluoride complexes of silver(III) are exemplified by the purple-red Cs2KAgF6 (elpasolite structure, octahedral Ag3+ paramagnetic with /x = 2.6/ub). Yellow MAgF4 (M = Na, Rb, K) and XeF AgF4 are diamagnetic and probably square planar [65],... 

The shielding tensor, and its diamagnetic and paramagnetic components, are not necessarily symmetric in the Cartesian indices [25-29], and the shielding tensor can in general be decomposed into a symmetric and an antisymmetric component, i.e. 

---