Transition elements characteristics

As regards the transition elements, the first row in particular show some common characteristics which define a substantial part of their chemistry the elements of the lanthanide and actinide series show an even closer resemblance to each other. 

These elements formed Group IIB of Mendeleef s original periodic table. As we have seen in Chapter 13, zinc does not show very marked transition-metaf characteristics. The other two elements in this group, cadmium and mercury, lie at the ends of the second and third transition series (Y-Cd, La-Hg) and, although they resemble zinc in some respects in showing a predominantly - - 2 oxidation state, they also show rather more transition-metal characteristics. Additionally, mercury has characteristics, some of which relate it quite closely to its immediate predecessors in the third transition series, platinum and gold, and some of which are decidedly peculiar to mercury. 

Reference has been made already to the existence of a set of inner transition elements, following lanthanum, in which the quantum level being filled is neither the outer quantum level nor the penultimate level, but the next inner. These elements, together with yttrium (a transition metal), were called the rare earths , since they occurred in uncommon mixtures of what were believed to be earths or oxides. With the recognition of their special structure, the elements from lanthanum to lutetium were re-named the lanthanons or lanthanides. They resemble one another very closely, so much so that their separation presented a major problem, since all their compounds are very much alike. They exhibit oxidation state -i-3 and show in this state predominantly ionic characteristics—the ions. 

Color Centers. Characteristics of a color center (1,3,7) include production by irradiation and destmction by heating. Exposure to light or even merely time in the dark may be sufficient to destroy these centers. Color arises from light absorption either from an electron missing from a normally occupied position, ie, a hole color center, or from an extra electron, ie, an electron color center. If the electron is a valence electron of a transition element, the term color center is not usually used. 

The various stoichiometries are not equally common, as can be seen from Fig. 6.5 the most frequently occurring are M2B, MB, MB2, MB4 and MBfi, and these five classes account for 75% of the compounds. At the other extreme RunBg is the only known example of this stoichiometry. Metal-rich borides tend to be formed by the transition elements whereas the boron-rich borides are characteristic of the more electropositive elements in Groups 1-3, the lanthanides and the actinides. Only the diborides MB2 are common to both classes. 

The three series of elements arising from the filling of the 3d, 4d and 5d shells, and situated in the periodic table following the alkaline earth metals, are commonly described as transition elements , though this term is sometimes also extended to include the lanthanide and actinide (or inner transition) elements. They exhibit a number of characteristic properties which together distinguish them from other groups of elements ... 

The most striking feature of the contrasts shown in Table 23-II is that the seventh-row elements display the multiplicity of oxidation states characteristic of transition elements rather than the drab chemistry of the +3 rare earth ions. Whereas Ce+3(aq) can be oxidized to Ce+4(aq) only with an extremely strong oxidizing agent, Th+Yaq) is the stable ion found in thorium salts and Th+3(aq) is unknown. In a similar... 

Low oxidation states - An important characteristic of transition metal chemistry is the formation of compounds with low (often zero or negative) oxidation states. This has little parallel outside the transition elements. Such complexes are frequently associated with ligands like carbon monoxide or alkenes. Compounds analogous to Fe(CO)s, [Ni(cod)2] (cod = 1,4-cyclooctadiene) or [Pt(PPh3]3] are very rarely encountered outside the transition-metal block. The study of the low oxidation compounds is included within organometallic chemistry. We comment about the nature of the bonding in such compounds in Chapter 6. 

Thus far, we have focused exclusively upon the block metals. For some, the term transition elements defines just these J-block species for others, it includes the rare earth or lanthanoid elements, sometimes called the inner transition elements . In this chapter, we compare the elements with respect to their valence shells. In doing so, we shall underscore concepts which we have already detailed as well as identifying both differences and similarities between certain aspects of main and inner transition-metal chemistry. We make no attempt to review lanthanoid chemistry at large. Instead our point of departure is the most characteristic feature of lanthanoid chemistry the +3 oxidation state. 

Oxidative addition reactions have been observed also for the binuclear clusters of other d-transition elements with multiple M-M bonds [1,116,117]. The multiplicity of the M-M bonds must decrease in these reactions. It is known from organic chemistry that similar reactions are extremely characteristic of unsaturated organic compounds. We believe that the capacity for oxidative... 

The principal characteristic of the transition elements is an incomplete electronic subshell that confers specific properties on the metal concerned. Ligand systems may participate in coordination not only by electron donation to the 3d levels in the first transition series but also by donation to incomplete outer 4s and 4p shells. Figure 5.1 shows that the differences in orbital energy levels between the 4s, 4p and 3d orbitals are much smaller than, for example, the difference between the inner 2s and 2p levels. Consequently, transitions between the 4s, 4p and 3d levels can easily take place and coordination is readily achieved. The manner in which ligand groups are oriented in surrounding the central metal atom is determined by the number and energy levels of the electrons in the incomplete subshells. 

Zinc, cadmium and mercury are at the end of the transition series and have electron configurations ndw(n + l)s2 with filled d shells. They do not form any compound in which the d shell is other than full (unlike the metals Cu, Ag and Au of the preceding group) these metals therefore do not show the variable valence which is one of the characteristics of the transition metals. In this respect these metals are regarded as non-transition elements. They show, however, some resemblance to the d-metals for instance in their ability to form complexes (with NH3, amines, cyanide, halide ions, etc.). 

Manganese represents the epitome of that characteristic property of the transition element namely the variable oxidation state. The aqueous solution chemistry includes all oxidation states from Mn(II) to Mn(VII), although these are of varying stability. Recently attention has been focused on polynuclear manganese complexes as models for the cluster of four manganese atoms which in conjunction with the donor side of Photosystem(II) is believed involved in plant photosynthetic oxidation of water. The Mn4 aggregate cycles between 6 distinct oxidation levels involving Mn(II) to Mn(IV). 

Scandium is the first element in the fourth period of the transition elements, which means that the number of protons in their nuclei increases across the period. As with all the transition elements, electrons in scandium are added to an incomplete inner shell rather than to the outer valence shell as with most other elements. This characteristic of using electrons in an inner shell results in the number of valence electrons being similar for these transition elements although the transition elements may have different oxidation states. This is also why all the transition elements exhibit similar chemical activity. 

Ruthenium also belongs to the platinum group, which includes six elements with similar chemical characteristics. They are located in the middle of the second and third series of the transition elements (groups 8, 9, and 10). The platinum group consists of ruthenium, rhodium, palladium, osmium, iridium, and platinum. 

As the first element in the third series of the transition elements, hafnium s atomic number ( jHf) follows the lanthanide series of rare-earths. The lanthanide series is separated out of the normal position of sequenced atomic numbers and is placed below the third series on the periodic table ( La to 7,Li). This rearrangement of the table allowed the positioning of elements of the third series within groups more related to similar chemical and physical characteristics—for example, the triads of Ti, Zr, and Hf V, Nb, andTa and Cu, Ag, and Au. 

Not all elements in these groups have the same properties and characteristics. For instance, in group 15, nitrogen is a gas, whereas the element just below it in group 15 is phosphorous, anon-metallic solid (semimetal). Just below phosphorous is arsenic (semimetal), followed by antimony and then bismuth, which are more metal-like. These last two, antimony and bismuth, are metals that might be considered an extension of periods 5 and 6 of the transition elements. 

There are several general ways to categorize elements in groups 13 to 16. These are metals different in several ways from the transition elements. They range from metallics (other metals) to metalloids (semiconductors) to nonmetals. The elements in these groups are arranged according to their properties, characteristics, and the position of their electrons in their atoms outer shells. These, and other factors, determine how they are depicted in the periodic table. 

Indium has one odd characteristic in that in the form of a sheet, like the metal tin, it will emit a shrieking sound when bent rapidly. Indium has some of the characteristics of other metals near it in the periodic table and may be thought of as an extension of the second series of the transition elements. Although it is corrosion-resistant at room temperature, it will oxidi2e at higher temperatures. It is soluble in acids, but not in alkalis or hot water. 

The lanthanide series is composed of metallic elements with similar physical properties, chemical characteristics, and unique structures. These elements are found in period 6, starting at group 3 of the periodic table. The lanthanide series may also be thought of as an extension of the transition elements, but the lanthanide elements are presented in a separate row of period 6 at the bottom of the periodic table. 

In aqueous solution, the reactivity of (34) is unique and does not have parallels among other transition-element nitrido complexes. For instance, a characteristic feature is the formation of [NTc(/r-0)TcN] + or [NTc(/u-0)2TcN] " structural units by hydrolysis (see Scheme 13). As observed with many high-valent M=0 species, substitution of halides by water leads to highly... 

Luminescence information on transition elements is substantially improved. Besides well known Mn + centers, emission of Mn was found and Mn + proposed as a possible participant in minerals luminescence. Luminescence characteristics of Mn +, Cr +, Ti +, Ni, Sb are presented and their... 

The first ionization energies of the elements are plotted in Figure 1.4. There is a characteristic pattern of the values for the elements Li to Ne which is repeated for the elements Na to Ar, and which is repeated yet again for the elements K, Ca and A1 to Kr (the s- and p-block elements of the fourth period). In the latter case, the pattern is interrupted by the values for the 10 transition elements of the d-block. The fourth period pattern is repeated by the fifth period elements, and there is an additional... 

The first electron attachment energies of the first 36 elements are plotted in Figure 1.5 and show the values for H and He followed by a characteristic pattern, the second repetition of which is split by the values for the 10 transition elements. The value for hydrogen is -72.8 kJ mol, which is very different from the Is orbital energy of -1312 kJ mol-1 because of the interelectronic repulsion term amounting to -72.8 -... 

Similar sorts of results may be found with the nitrate anion. In this case, the nitrate ion itself has a characteristic absorption in the ultraviolet. When paired with a transition-element cation, in alcoholic solution, this absorption is markedly altered (2). It also shows alterations with other cations. In certain ketone and ether solutions, it has been possible to demonstrate further that the vibrational spectrum of the nitrate ion has been altered in such a pattern as to be consistent with a binding of one of the nitrate oxygens to the cation (2), so that major vibration now occurs between this oxygen and the rest of the bound nitrate group. 

The "d" block elements "B" Croups (Columns 3-12). the transition metals Characteristically, atoms of these elements in their ground states have electron configurations that are filling d orbitals 17 For example, the first transition series proceeds from Sc(4i33d1) to Zn(4i,23d10). Each of these ten elements stands at the head of a family of congeners (e.g the chromium family, V1B, 6). 

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