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Potassium and sodium were first isolated in 1807 by Davy as products of the electrolysis of molten KOH and NaOH. In 1817, Arfvedson recognized similarities between the solubilities of compounds of lithium and those of sodium and potassium. The following year, Davy also isolated lithium by electrolysis of molten Li2O . ... | {
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The alkali metals are very similar in their chemical properties, which are governed by the ease with which they can lose one electron (the alkali metals have the lowest ionization energies of all the elements) and achieve a noble gas configuration. All are excellent reducing agents. The metals react vigorously with wat... | {
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The largest of the alkali metal cations, Cs<sup>+</sup>, is trapped most effectively by the largest cryptand ([3.2.2]), and the smallest, Li<sup>+</sup>, by the smallest cryptand ([2.1.1]).\*\* Related correlations are in Figure 8.7. Cryptands play a vital role in the study of alkali metal anions (alkalides).
![](_... | {
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Magnesium and calcium compounds have been used since antiquity. The ancient Romans used mortars containing lime (CaO) mixed with sand, and ancient Egyptians used gypsum
**FIGURE 8.8** (a) $Cs^{+}(15C5)_{2}e^{-}$ , a crown ether electride. The cesium cation is bound to the oxygen atoms ... | {
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The Group 2 elements, with the exception of beryllium, have very similar chemical properties; much of their chemistry is governed by their tendency to lose two electrons to achieve a noble gas electron configuration. The Group 2 elements are good reducing agents.
| Element | lonization<br>Energy<br>(kJ mol <sup>—1</s... | {
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Elements in this group include one nonmetal, boron, and four elements that are primarily metallic. Physical properties of these elements are shown in **Table 8.5**.
#### **Boron**
Boron's chemistry is so different from that of the other elements in this group that it deserves separate discussion. Chemically, boron ... | {
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$$\begin{array}{c} H \\ B \\ C \\ H \\ B \\ H \\ C_2B_3H_5 \end{array}$$
on each C and B)
Carboranes
$$H_3C$$
$C$
$CH_3$
$C_6H_5$
$C_6H_5$
$C_6H_5$
$C_6H_5$
$C_6H_5$
$C_6H_5$
$C_6H_5$
Bridged aluminum compounds
The boranes, carboranes, and rela... | {
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The boron trihalides, $BX_3$ , are Lewis acids (Chapter 6). These compounds are monomeric and planar—unlike diborane, $B_2H_6$ , and the aluminum halides, $Al_2X_6$ (Section 3.1.4). As Lewis acids, boron trihalides can accept an electron pair from a halide to form tetrahaloborate ions, $BX_4^-$ . Boron halide cata... | {
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Group 14 elements range from a nonmetal, carbon, to the metals tin and lead, with the intervening elements showing semimetallic behavior. Carbon has been known from prehistory as the charcoal resulting from partial combustion of organic matter. Diamonds have been prized as precious gems for thousands of years. Neither ... | {
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Carbon was encountered primarily in two allotropes, diamond and graphite, until 1985. The diamond structure is rigid, with each atom surrounded tetrahedrally by four other atoms in a structure that has a cubic unit cell. As a result, diamond is extremely hard, the hardest of all naturally occurring substances. Graphite... | {
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"Header 3": "**Diamond and Graphite**",
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Graphite consists of multiple layers of carbon atoms ( Figure 8.18 ). A single, isolated layer is called **graphene** , also shown in the figure. First prepared in 2004, 22 graphene has been the center of considerable research, both to study its properties and to develop efficient ways to prepare graphene sheets. Graph... | {
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"Header 3": "**Graphene**",
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Graphene can be cut into thin strips, dubbed **nanoribbons** , by lithographic techniques. 26 These ribbons are described by their edges, either *zigzag* or *armchair* ( **Figure 8.19** ). If the nanoribbons are sufficiently narrow, they have a band gap between their conduction and valence bands. As in the case of quan... | {
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"Header 3": "**Nanoribbons and Nanotubes**",
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Graphene is by no means the only possible two-dimensional arrangement of carbon. Recently a variety of planar structures containing carbon—carbon triple bonds, graphynes, have been proposed and considerable effort has been devoted to preparing them. Examples of these structures are in Figure 8.23.
The "extraordinary"... | {
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"Header 3": "Graphyne",
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The diameter of $C_{60}$ is 3.7 Å. Endofullerenes feature atoms or molecules trapped (or encapsulated) inside, including metal ions, noble gases, nitrogen atoms, and hydrogen gas. A remarkable synthetic achievement was the synthesis of $H_2O@C_{60}$ ,\* where a single water molecule is trapped inside $C_{60}$ (**F... | {
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"Header 3": "Endofullerenes<sup>48</sup>",
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A common misconception is that carbon is limited to 4-coordination. Although carbon is bonded to four or fewer atoms in the vast majority of its compounds, many examples are known in which carbon has coordination numbers of 5, 6, or higher. 5-coordinate carbon is common, with methyl and other groups frequently forming ... | {
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"Header 3": "8.6.2 Compounds",
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Since the beginning of the Industrial Revolution, the carbon dioxide concentration in the atmosphere has increased substantially, an increase that will continue indefinitely unless major policy changes are made by the industrialized nations. The consequences of a continuing increase in atmospheric $CO_2$ are difficul... | {
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"Header 3": "8.6.2 Compounds",
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Nitrogen is the most abundant component of Earth's atmosphere (78.1% by volume). However, the element was not isolated until 1772, when Rutherford, Cavendish, and Scheele removed oxygen and carbon dioxide from air. Phosphorus was first isolated from urine by Brandt in 1669. Because the element glowed in the dark on exp... | {
"Header 1": "8.7 Group 15",
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For example, the heavier Group 15 elements form structurally characterized anions $[E(N_3)_4]^-$ (E = As, Sb) and $[Bi(N_3)_5(DMSO)]^-$ (Figure 8.30).<sup>66</sup>
Although $C_2^{2-}$ and $O_2^{2-}$ were long known, $N_2^{2-}$ (diazenide) was not characterized until 2001.<sup>67</sup> In SrN<sub>2</sub>, th... | {
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In addition to ammonia, nitrogen forms the hydrides N<sub>2</sub>H<sub>4</sub> (hydrazine), N<sub>2</sub>H<sub>2</sub> (diazene or diimide), and HN<sub>3</sub> (hydrazoic acid) (Figure 8.31).
Ammonia is of immense industrial importance. More than 80 percent of the ammonia produced is used in fertilizers, with additio... | {
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Nitrogen oxides and ions containing nitrogen and oxygen are summarized in **Table 8.10**. Nitrous oxide, $N_2O$ , is used as a dental anesthetic and an aerosol propellant. On atmospheric decomposition, $N_2O$ yields its innocuous parent gases and is an environmentally acceptable substitute for chlorofluorocarbons. O... | {
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Show whether the decomposition of $NH_4NO_3$ (2 $NH_4NO_3 \longrightarrow 2 N_2 + O_2 + 4 H_2O$ ) can be a spontaneous reaction, based on the potentials given in Appendix B.7, by determining both $E^{o}$ and $\Delta G^{o}$ .
Among acids, phosphoric acid, H<sub>3</sub>PO<sub>4</sub>, is second only to sulfuric a... | {
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The first two group 16 elements are familiar as O<sub>2</sub>, the colorless gas that comprises about 21 percent of Earth's atmosphere, and sulfur, a nonmetallic yellow solid. The third element, selenium, is important in the xerography process. A brilliant red formed by a combination of CdS and CdSe is used in colored ... | {
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Oxygen exists primarily in the diatomic form O2, but traces of ozone, O3, are found in the upper atmosphere and in the vicinity of electrical discharges. O2 is paramagnetic and O3 is diamagnetic. The paramagnetism of O2 is the consequence of two electrons with parallel spin occupying p\*(2*p*) orbitals ( Section 5.2.3 ... | {
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"Header 3": "**Oxygen**",
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More allotropes are known for sulfur than for any other element, with the most stable form at room temperature (orthorhombic, $\alpha$ -S<sub>8</sub>) having eight sulfur atoms arranged in a puckered ring. **Figure 8.35** shows three of the most common sulfur allotropes.<sup>83</sup>
Heating sulfur results in intere... | {
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"Header 3": "**Sulfur**",
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85 The ability to catalyze nitrogen fixation and the reduction of hydrogen ions to hydrogen gas under mild conditions on an
TABLE 8.13 Molecules and Ions Containing Sulfur and Oxygen
| Formula | Name | Structure <sup>a</sup> | Notes ... | {
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Van Helmont first recognized chlorine as a gas in approximately 1630. Scheele conducted care[ful studies on chl](#page-6-0)orine in the 1770s (hydrochloric acid, which was used in these syntheses, had been prepared by alchemists around 900 ce ). Iodine was obtained by Courtois in 1811 by subliming the product of the re... | {
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As the concentration of HF increases, however, its tendency to form H<sub>3</sub>O<sup>+</sup> increases as a result of further reaction of this ion pair with HF.
$$H_3O^+F^- + HF \Longrightarrow H_3O^+ + HF_2^-$$
This view is supported by X-ray crystallographic studies of the ion pairs H<sub>3</sub>O<sup>+</sup>F<... | {
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In addition to the common monatomic halide ions, numerous polyatomic species, both cationic and anionic, have been prepared. The brown triiodide ion, $I_3^-$ , is formed from $I_2$ and $I^-$ :
$$I_2 + I^- \rightleftharpoons I_3^ K \approx 698$$
at 25 °C in aqueous solution
Other polyiodide ions have been charac... | {
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"Header 3": "**Polyatomic Ions**",
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Halogens form many compounds containing two or more different halogens. Like the halogens themselves, these may be diatomic, such as CIF, or polyatomic, such as CIF<sub>3</sub>, BrF<sub>5</sub>, or IF<sub>7</sub>. Many polyatomic ions containing two or more halogens have been synthesized. **Table 8.15** lists neutral (... | {
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Parallels have been observed between the chemistry of the halogens and other dimeric species. Dimeric molecules showing considerable similarity to the halogens are often called **pseudohalogens**. Chapter 15 considers parallels between the halogens and pseudohalogens, including examples from organonmetallic chemistry. ... | {
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"Header 3": "**Pseudohalogens**",
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Cavendish obtained the first experimental evidence for the noble gases in 1766. In a series of experiments on air, he was able to sequentially remove nitrogen (then known as "phlogisticated air"), oxygen ("dephlogisticated air"), and carbon dioxide ("fixed air") from air
<sup>\*</sup>For additional examples of pseudo... | {
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The group 18 elements were once believed to be totally unreactive as a consequence of the very stable "octet" valence electron configurations of their atoms. Their chemistry was simple: they had none!
The first chemical compounds containing noble gases to be discovered were **clathrates**, "cage" compounds in which n... | {
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The structure of XeF<sub>8</sub><sup>2-</sup> is slightly distorted; it is an approximate square antiprism $(D_{4d}$ symmetry), but with one face slightly larger than the opposite face, resulting in approximate $C_{4\nu}$ symmetry (Figure 8.40).<sup>101</sup> Although this distortion may be a consequence of the w... | {
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116 A rare example of KrF<sub>2</sub> serving a ligand was observed in [BrOF<sub>2</sub>][AsF<sub>6</sub>] • 2 KrF<sub>2</sub> (**Figure 8.45c**).<sup>117</sup> Examples of bonding to elements other than fluorine include $[F-Kr-N \equiv CH]^+AsF_6^{-,118} Kr(OTeF_5)_2$ , <sup>119</sup> and HKrCCH. <sup>120</sup>
Sig... | {
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- G. J. Leigh, ed., Nomenclature of Inorganic Chemistry, Recommendations 1990, International Union of Pure and Applied Chemistry, Blackwell Scientific Publications, Oxford UK, pp. 41–43.
- L. C. Allen, J. E. Huheey, J. Inorg. Nucl. Chem., 1980, 42, 1523; T. L. Meek, J. Chem. Educ., 1995, 72, 17.
- W. M. Latimer, Oxidat... | {
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"Header 3": "References",
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Prato, *Chem. Rev.* , **2006** , *106* , 1105.
- **35.** D. Malko, C. Neiss, F. Viñes, A. Görling, *Phys. Rev. Lett.* , **2012** , *108* , 086804.
- **36.** G. Li, Y. Li, H. Liu, Y. Guo, Y. Li, D. Zhu, *Chem. Commun.* , **2010** , *46* , 3256.
- **37.** K. Srinivasu, S. K. Ghosh, *J. Phys. Chem. C* , **2012** , *116* ,... | {
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M. Cossairt, C. C. Cummins, *J. Am. Chem. Soc.* , **2009**, *131* , 15501.
- **65.** D. Fischer, M. Jansen, *Angew. Chem. Int. Ed.* , **2002** , *41* , 1755. G. V. Vajenine, *Inorg. Chem.* , **2007** , *46* , 5146
- **66.** A. Schulz, A. Villinger, *Chem. Eur. J.* , **2012** , *18* , 2902.
- **67.** G. Auffermann, Y.... | {
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Ebsworth, D. W. H. Rankin, and S. Craddock, *Structural Methods in Inorganic Chemistry* , Blackwell Scientifi c Publications, Oxford, 1987, pp. 397–398.
- **99.** D. A. Dixon, W. A. de Jong, K. A. Peterson, K. O. Christe, G. J. Schrobilgen, *J. Am. Chem. Soc.* , **2005** , *127* , 8627.
- **100.** S. Hoyer, T. Emmler, ... | {
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More detailed descriptions of the chemistry of the main group elements can be found in N. N. Greenwood and A. Earnshaw, *Chemistry of the Elements*, 2nd ed., Butterworth-Heinemann, London, 1997, and in F. A. Cotton, G. Wilkinson, C. A. Murillo, and M. Bochman, *Advanced Inorganic Chemistry*, 6th ed., Wiley InterScience... | {
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"Header 3": "**General References**",
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- **8.1** The ions $H_2^+$ and $H_3^+$ have been observed in gas discharges.
- **a.** $H_2^+$ has been reported to have a bond distance of 106 pm and a bond dissociation enthalpy of 255 kJ mol<sup>-1</sup>. Comparable values for the neutral molecule are 74.2 pm and 436 kJ mol<sup>-1</sup>. Are these values for $... | {
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"Header 3": "**Problems**",
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Soc.*, **2012**, *134*, 4461.
- **8.20** Explain the increasing stability of the 2+ oxidation state for the Group 14 (IVA) elements with increasing atomic number.
**8.21** 1,2-Diiododisilane has been observed in both *anti* and *gauche* conformations. (See K. Hassler, W. Koell, K. Schenzel, *J. Mol. Struct.*, **1995*... | {
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On the basis of frontier orbitals (identify them), account for the difference in their colors.
- **8.38** $I_2^+$ exists in equilibrium with its dimer $I_4^{2+}$ in solution. $I_2^+$ is paramagnetic and the dimer is diamagnetic. Crystal structures of compounds containing $I_4^{2+}$ have shown this ion to be pla... | {
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Soc.*, **2009**, *131*, 4173.)
- **a.** What is the bond order in [XeF]<sup>+</sup>?
- b. Of compounds 1 through 4, which has the longest S—N distance? The shortest?
- c. Which of the compounds 1 through 4 is most likely to have linear bonding around the nitrogen atom?
- **d.** By the VSEPR approach, is the bonding aro... | {
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- **8.54** It has been proposed that salts containing the cation [FBeNg]<sup>+</sup>, where Ng = He, Ne, or Ar, may be stable. Use molecular modeling software to calculate and display the molecular orbitals of [FBeNe]<sup>+</sup>. Which molecular orbitals would be the primary ones engaged in bonding in this ion? (See M... | {
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Although the formal study of coordination compounds really begins with Alfred Werner (1866–1919), coordination compounds have been used as pigments and dyes since antiquity. Examples include Prussian blue (KFe[Fe(CN)6]), aureolin (K3[Co(NO2)6] # 6H2O, yellow), and alizarin red dye (the calcium aluminum salt of 1,2-dihy... | {
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For example, he was able to synthesize only two isomers of $[\text{Co(NH}_3)_4\text{Cl}_2]^+$ . Possible structures with six ligands are hexagonal, hexagonal pyramidal, trigonal prismatic, trigonal antiprismatic, and octahedral. Because there are two possible isomers for the octahedral shape and three for each of the ... | {
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The nomenclature of coordination chemistry has changed over time. The older literature features multiple nomenclature styles. Contemporary rules used for naming coordination compounds are discussed in this chapter. More complete sources are available to explore classic nomenclature approaches necessary to examine older... | {
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| Formula |
| bidentate | ethylenediamine | 1,2-ethanediamine ... | {
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**1.** The cation comes first, followed by the anion.
**Examples:** diamminesilver(I) chloride, [Ag(NH3)2]Cl potassium hexacyanoferrate(III), K3[Fe(CN)6]
**2.** The inner coordination sphere is enclosed in square brackets. Although the metal is provided first within the brackets, the ligands within the coordination... | {
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Give the structures of these coordination complexes:
- **a.** Tris(acetylacetonato)iron(III)
- **b.** Hexabromoplatinate(2–)
- **c.** Potassium diamminetetrabromocobaltate(III)
- **d.** Tris(ethylenediamine)copper(II) sulfate
- e. Hexacarbonylmanganese(I) perchlorate
- **f.** Ammonium tetrachlororuthenate(1–)
Cl NH... | {
"Header 1": "9.2 **[Nomenclature](#page-7-0)**",
"Header 3": "**EXERCISE 9.2**",
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The variety of coordination numbers in these complexes provides a large number of **isomers** . As the coordination number increases so does the number of possible isomers. We will focus on the common coordination numbers, primarily 4 and 6. We will not discuss isomerism where the ligands *themselves* are isomers. For ... | {
"Header 1": "9.3 **[Isomerism](#page-7-0)**",
"token_count": 227,
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*Cis* and *trans* isomers of square-planar complexes are common; many platinum(II) examples are known. The isomers of [Pt(NH3)2Cl2] are shown in Figure 9.5 . The *cis* isomer is used in medicine as the antitumor agent cisplatin. Chelate rings can enforce a *cis* structure if the chelating ligand is too small to span th... | {
"Header 1": "9.3.2 **[4-Coordinate Complexes](#page-7-0)**",
"token_count": 317,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Chiral molecules have nonsuperimposable mirror images, a condition that can be expressed in terms of symmetry elements. A molecule is chiral only if it has no rotation-reflection $(S_n)$ axes.\* This means that chiral molecules (Section 4.4.1) either have no symmetry elements (except identity, $C_1$ ) or have only ax... | {
"Header 1": "9.3.3 Chirality",
"token_count": 266,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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ML<sub>3</sub>L'<sub>3</sub> complexes where L and L' are monodentate ligands, have two isomers called fac-(facial) and mer- (meridional). Fac isomers have three identical ligands on one triangular face; mer isomers have three identical ligands in a plane bisecting the molecule. Similar isomers are possible with chelat... | {
"Header 1": "9.3.4 6-Coordinate Complexes",
"token_count": 2025,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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The notation <ab> indicates that a and b are *trans* to each other; M is the metal; and a, b, c, d, e, and f are monodentate ligands. The six octahedral positions are commonly numbered as in Figure 9.12 , with positions 1 and 6 in axial positions and 2 through 5 in counterclockwise order as viewed from the 1 position. ... | {
"Header 1": "9.3.4 6-Coordinate Complexes",
"token_count": 1228,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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The isomers of Ma<sub>2</sub>b<sub>2</sub>c<sub>2</sub> can be found by Bailar's method. In each row below, the first pair of ligands is held constant: <aa>, <ab>, and <ac> in rows 1, 2, and 3, respectively. In column B, one component of the second pair is traded for a component of the third pair (for example, in row 2... | {
"Header 1": "9.3.4 6-Coordinate Complexes",
"Header 3": "**EXAMPLE 9.1**",
"token_count": 281,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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A methodical approach is important in finding isomers. Consider M(AA)(BB)cd. AA and BB must be in *cis* positions, because they are linked in the chelate ring. For M(AA)(BB)cd, we first try c and d in *cis* positions. One A and one B must be *trans* to each other:
$$\begin{array}{cccccccccccccccccccccccccccccccccccc$... | {
"Header 1": "9.3.4 6-Coordinate Complexes",
"Header 3": "**EXAMPLE 9.2**",
"token_count": 336,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Before discussing nomenclature rules for ring geometry, we need to establish the handedness of propellers and helices. Consider the propellers in **Figure 9.13**. The first is a left-handed propeller; rotating it *counterclockwise* in air or water would move it away from the observer. The second, a right-handed propell... | {
"Header 1": "9.3.5 Combinations of Chelate Rings",
"token_count": 1094,
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Because many chelate rings are not planar, they can have different conformations in different molecules, even in otherwise identical molecules. In some cases, these different conformations are also chiral. The notation used in these situations requires using two lines to establish the handedness and the labels $\lambd... | {
"Header 1": "9.3.6 Ligand Ring Conformation",
"token_count": 1323,
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Hydrate isomerism requires water to play two roles, as (1) a ligand and as (2) an additional occupant (or solvate) within the crystal structure.\* *Solvent isomerism* broadens the definition to allow for the possibility of ammonia or other ligands participating as solvates.
$CrCl_3 \cdot 6 \ H_2O$ is a classic examp... | {
"Header 1": "9.3.7 Constitutional Isomers",
"Header 3": "**Hydrate Isomerism**",
"token_count": 1141,
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The definition of coordination isomerism depends on the context. Historically, a complete series of coordination isomers required at least two metals. The ligand:metal ratio remains the same, but the ligands attached to a specific metal ion change. For the empirical formula Pt(NH<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub>,... | {
"Header 1": "9.3.7 Constitutional Isomers",
"Header 3": "**Coordination Isomerism**",
"token_count": 758,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Ligands such as thiocyanate, SCN $^-$ , and nitrite, NO $_2^-$ , can bond to the metal through different atoms. Class (a) metal ions (hard acids) tend to bond to the thiocyanate nitrogen and class (b) metal ions (soft acids) bond through the thiocyanate sulfur. Solvent can also influence the point of attachment. Compou... | {
"Header 1": "9.3.7 Constitutional Isomers",
"Header 3": "Linkage (Ambidentate) Isomerism",
"token_count": 624,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Fractional crystallization can separate geometric isomers. This strategy assumes that the isomers will exhibit appreciably different solubilities in a specific solvent mixture, and that the isomers will not co-crystallize. For complex cations and anions, alternate counterions can be introduced (via a process called *me... | {
"Header 1": "9.3.8 **[Separation and Identification of Isomers](#page-7-0)**",
"token_count": 1668,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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The isomers described to this point have had octahedral or square-planar geometry. In this section, we describe other geometries. Explanations for some of the shapes are consistent with VSEPR predictions (Chapter 3), with the general assumption that the metal d electrons are stereochemically inactive. In these cases, 3... | {
"Header 1": "9.4 Coordination Numbers and Structures",
"token_count": 319,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Coordination number 1 is rare for complexes in condensed phases (solids and liquids). Attempts to prepare species in solution with only one ligand are generally futile; solvent molecules often coordinate, resulting in higher coordination numbers. Two organometallic compounds with coordination number 1 are the Tl(I) (Fi... | {
"Header 1": "9.4.1 Coordination Numbers 1, 2, and 3",
"token_count": 1953,
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Tetrahedral and square-planar structures are common.<sup>53</sup> Another structure, with four bonds and one lone pair, appears in main group compounds—such as SF<sub>4</sub> and TeCl<sub>4</sub> —giving a "seesaw" geometry (Chapter 3). Many $d^0$ and $d^{10}$ complexes have tetrahedral
$$\begin{array}{cccccccccc... | {
"Header 1": "9.4.1 Coordination Numbers 1, 2, and 3",
"Header 3": "9.4.2 Coordination Number 4",
"token_count": 1223,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Coordination number 5 includes trigonal bipyramidal, square pyramidal, and pentagonal planar complexes. Pentagonal planar complexes are extremely rare; only the main group ions $[XeF_5]^{-(58)}$ and $[IF_5]^{2-(59)}$ are known. The energy difference between the trigonal bipyramidal and square pyramidal structures i... | {
"Header 1": "9.4.3 Coordination Number 5",
"token_count": 566,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Six is the most common coordination number. The most common structure is octahedral, but trigonal prismatic structures are also known. Octahedral compounds exist for $d^0$ to $d^{10}$ transition metals. Many compounds with octahedral structures have already been displayed as examples in this chapter. Others include... | {
"Header 1": "9.4.3 Coordination Number 5",
"Header 3": "9.4.4 Coordination Number 6",
"token_count": 1449,
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Three structures are possible for 7-coordinate complexes, the pentagonal bipyramid, capped trigonal prism, and capped octahedron. <sup>69</sup> In the capped shapes, the seventh ligand is simply added to a face of the core structure, with necessary adjustments in the other angles to accommodate the additional ligand. A... | {
"Header 1": "9.4.5 Coordination Number 7",
"token_count": 770,
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Although a central atom or ion within a complex where each donor atom defined the corner of a cube would be 8-coordinate, this structure exists only in ionic lattices such as CsCl, and not in discrete molecular species. However, 8-coordinate square antiprismatic and dodecahedral geometries are common.<sup>74</sup> 8-co... | {
"Header 1": "9.4.5 Coordination Number 7",
"Header 3": "9.4.6 Coordination Number 8",
"token_count": 726,
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Coordination numbers are known up to 16.82 Many examples of 9-coordinate lanthanides and actinides, atoms with energetically accessible f orbitals, are known.<sup>83</sup> 9-coordinate highly luminescent lanthanide complexes, including those containing europium (example in Figure 9.35a), are of current interest. 84 The... | {
"Header 1": "9.4.7 Larger Coordination Numbers",
"token_count": 544,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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To this point, coordination complexes that are individual entities that pack together in the solid state and exist as separated units in solution have been our focus. A burgeoning area of inorganic chemistry is the synthesis and application of substances in which ligands act as bridges to create extended structures in ... | {
"Header 1": "9.5 Coordination Frameworks",
"token_count": 2048,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Kauffman, Classics in Coordination Chemistry, Part 1, New York, 1968.
- **4.** L. Pauling, *J. Chem. Soc.*, **1948**, 1461; *The Nature of the Chemical Bond*, 3rd ed., Cornell University Press, Ithaca, NY, 1960, pp. 145–182.
- 5. J. S. Griffith, L. E. Orgel, Q. Rev. Chem. Soc., 1957, XI, 381.
- **6.** Pauling, *The Nat... | {
"Header 1": "9.5 Coordination Frameworks",
"token_count": 1997,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Hawkins, Absolute Configuration of Metal Complexes, Wiley InterScience, New York, 1971, p. 156.
- M. Niemeyer, P. P. Power, Angew. Chem., Int. Ed., 1998, 37, 1277; S. T. Haubrich, P. P. Power, J. Am. Chem. Soc., 1998, 120, 2202.
- H. V. Rasika Dias, S. Singh, T. R. Cundari, *Angew. Chem.*, Int. Ed., 2005, 44, 4907.
- A... | {
"Header 1": "9.5 Coordination Frameworks",
"token_count": 1983,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Drew, A. P. Wolters, *Chem. Commun* ., **1972** , 457.
- **72.** S. Ye, F. Neese, A. Ozarowski, D. Smirnov, J. Krzystek, J. Telser, J.-H. Liao, C.-H. Hung, W.-C. Chu, Y.-F. Tsai, R.-C. Wang, K.-Y. Chen, H.-F. Hsu, *Inorg. Chem.* , **2010** , *49* , 977.
- **73.** D. Casanova, P. Alemany, J. M. Bofi ll, S. Alvarez, *C... | {
"Header 1": "9.5 Coordination Frameworks",
"token_count": 1974,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Chem.*, 1995, 34, 757.
- S. R. Halper, M. R. Malachowski, H. M. Delaney, and S. M. Cohen, *Inorg. Chem.*, 2004, 43, 1242.
- 100. K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. R. Bloch, Z. R. Herm, T.-H. Bae, J. R. Long, Chem. Rev., 2012, 112, 724. J.-R. Li, R. J. Kuppler, H.-C. Zhou, Chem. Soc. Rev., 2009, 38... | {
"Header 1": "9.5 Coordination Frameworks",
"token_count": 531,
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The official documents on IUPAC nomenclature are G. J. Leigh, editor, *Nomenclature of Inorganic Chemistry*, Blackwell Scientific Publications, Oxford, England, 1990 and J. A. McCleverty and N. G. Connelly, editors, *IUPAC*, *Nomenclature of Inorganic Chemistry II: Recommendations 2000*, Royal Society of Chemistry, Cam... | {
"Header 1": "9.5 Coordination Frameworks",
"Header 3": "**General References**",
"token_count": 277,
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- **9.1** By examining the symmetry, determine if any of the first four proposed structures for hexacoordinate complexes in Figure 9.3 would show optical activity.
- **9.2** Give chemical names for the following:
- a. [Fe(CN)<sub>2</sub>(CH<sub>3</sub>NC)<sub>4</sub>]
- **b.** Rb[AgF<sub>4</sub>]
- **c.** [Ir(CO)Cl(PPh... | {
"Header 1": "9.5 Coordination Frameworks",
"Header 3": "**Problems**",
"token_count": 2040,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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In addition to cubanes in which all metals and nonmetals are identical, they have been prepared with more than one metal and/or more nonmetal in the central 8-atom core; attached groups on the outside may also vary.
- **a.** How many isomers are possible if the core has the following formulas:
- **1.** Mo<sub>3</su... | {
"Header 1": "9.5 Coordination Frameworks",
"Header 3": "**Problems**",
"token_count": 1794,
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A critical objective of any bonding theory is to explain the energies of chemical compounds. Inorganic chemists frequently use **stability constants**, sometimes called **formation constants**, as indicators of bonding strength. These are equilibrium constants for reactions that form coordination complexes. Here are tw... | {
"Header 1": "10.1.1 Thermodynamic Data",
"token_count": 1786,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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The complexation of Cd<sup>2+</sup> with methylamine and ethylenediamine are compared in Table 10.2 for:
$$\begin{split} [\text{Cd}(\text{H}_2\text{O})_6]^{2^+} + 4 & \text{CH}_3\text{NH}_2 & \longrightarrow & [\text{Cd}(\text{CH}_3\text{NH}_2)_4(\text{H}_2\text{O})_2]^{2^+} + 4 \text{ H}_2\text{O} \\ & \text{(no c... | {
"Header 1": "10.1.1 Thermodynamic Data",
"token_count": 1094,
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The magnetic properties of a coordination compound can provide indirect evidence of its orbital energy levels, similarly to that described for diatomic molecules in Chapter 5. Hund's rule requires the maximum number of unpaired electrons in energy levels with equal, or nearly equal, energies. Diamagnetic compounds, wit... | {
"Header 1": "10.1.2 Magnetic Susceptibility",
"token_count": 755,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Calculate L and S for the nitrogen atom.
The magnetic moment in terms of S and L is
$$\mu_{S+L} = g\sqrt{[S(S+1)] + [\frac{1}{4}L(L+1)]}$$
where
$\mu = \text{magnetic moment}$
g = gyromagnetic ratio (conversion to magnetic moment)
S = spin quantum number
L =orbital quantum number
Although detailed elect... | {
"Header 1": "10.1.2 Magnetic Susceptibility",
"Header 3": "**EXERCISE 10.1**",
"token_count": 1028,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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The Gouy method<sup>3</sup> is a traditional approach for determining magnetic susceptibility. This method, rarely used in modern laboratories, requires an analytical balance and a small magnet (Figure 10.1).<sup>4</sup> The solid sample is packed into a glass tube. A small high-field U-shaped magnet is weighed four ti... | {
"Header 1": "10.1.2 Magnetic Susceptibility",
"Header 3": "**Measuring Magnetic Susceptibility**",
"token_count": 838,
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Paramagnetism and diamagnetism represent only two types of magnetism. These substances only become magnetized when placed in an external magnetic field. However, when most people think of magnets, for example those that attach themselves to iron, they are envisioning a persistent magnetic field without the requirement ... | {
"Header 1": "10.1.2 Magnetic Susceptibility",
"Header 3": "**Ferromagnetism and Antiferromagnetism**",
"token_count": 230,
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Evidence of orbital energy levels can be obtained from electronic spectra. The energy of the photons absorbed as electrons are raised to higher levels is the difference in energy between
<sup>\*</sup> An inexpensive approach is to place a sealed capillary tube containing the solution of the reference solute in a stan... | {
"Header 1": "10.1.3 **[Electronic Spectra](#page-7-0)**",
"token_count": 281,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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This is a method of estimating the relative magnitudes of molecular orbital energies within coordination complexes. It explicitly takes into account the orbitals responsible for ligand binding as well as the relative orientation of the frontier orbitals.
Modern computational chemistry allows calculations to predict g... | {
"Header 1": "10.2 **[Bonding Theories](#page-7-0)**",
"Header 3": "**Angular Overlap Method**",
"token_count": 302,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Crystal field theory was originally developed to describe the electronic structure of metal ions in crystals, where they are surrounded by anions that create an electrostatic field with symmetry dependent on the crystal structure. The energies of the d orbitals of the metal ions are split by the electrostatic field, an... | {
"Header 1": "10.2.1 Crystal Field Theory",
"token_count": 842,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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For octahedral complexes, ligands can interact with metals in a sigma fashion, donating electrons directly to metal orbitals, or in a pi fashion, with ligand-metal orbital interactions occurring in two regions off to the side. Examples of such interactions are shown in Figure 10.3.
As in Chapter 5, we will first cons... | {
"Header 1": "10.3.1 Molecular Orbitals for Octahedral Complexes",
"token_count": 823,
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The basis for a reducible representation is a set of six donor orbitals on the ligands as, for example, $\sigma$ -donor orbitals on six NH<sub>3</sub> ligands.\* Using this set as a basis—or equivalently
Sigma bonding interaction between two ligand orbitals and metal $d_{z2}$ orbita... | {
"Header 1": "10.3.1 Molecular Orbitals for Octahedral Complexes",
"Header 3": "Sigma Interactions",
"token_count": 769,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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The d orbitals play key roles in transition-metal coordination chemistry, so it is useful to examine them first. According to the $O_h$ character table, the d orbitals match the irreducible representations $E_g$ and $T_{2g}$ . The $E_g$ ( $d_{x^2-y^2}$ and $d_{z^2}$ ) orbitals match the $E_g$ ligand orbitals... | {
"Header 1": "10.3.1 Molecular Orbitals for Octahedral Complexes",
"Header 3": "The d Orbitals",
"token_count": 310,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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The valence s and p orbitals of the metal have symmetry that matches the two remaining irreducible representations: s matches $A_{1g}$ and the set of p orbitals matches $T_{1u}$ . Because of the symmetry match, the $A_{1g}$ interactions lead to the formation of bonding and antibonding orbitals $(a_{1g}$ and $a_... | {
"Header 1": "10.3.1 Molecular Orbitals for Octahedral Complexes",
"Header 3": "The s and p Orbitals",
"token_count": 960,
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Although Figure 10.5 can be used as a guide to describe energy levels in octahedral transition-metal complexes, it must be modified when ligands that can engage in pi interactions with metals are involved; pi interactions can have dramatic effects on the $t_{2g}$ orbitals.
<sup>\*</sup>Recall that in transition met... | {
"Header 1": "10.3.1 Molecular Orbitals for Octahedral Complexes",
"Header 3": "Pi Interactions",
"token_count": 721,
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Verify the characters of $\Gamma_{\pi}$ and that it reduces to $T_{1g} + T_{2g} + T_{1u} + T_{2u}$ .
The most important consequence of this analysis is that it generates a representation that has $T_{2g}$ symmetry, a match for the $T_{2g}$ set of orbitals $(d_{xy}, d_{xz}, and d_{yz})$ that is nonbonding for... | {
"Header 1": "10.3.1 Molecular Orbitals for Octahedral Complexes",
"Header 3": "**EXERCISE 10.5**",
"token_count": 2023,
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Figure 10.10(a) is representative of $[Cr(CN)_6]^{3-}$ and Figure 10.10(b) is representative of [CrF<sub>6</sub>]<sup>3-</sup>.
described as **ligand-to-metal** (L $\longrightarrow$ M) $\pi$ bonding, with the $\pi$ electrons from the ligands being donated to the metal ion. Ligands participating in such intera... | {
"Header 1": "10.3.1 Molecular Orbitals for Octahedral Complexes",
"Header 3": "**EXERCISE 10.5**",
"token_count": 622,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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In octahedral coordination complexes, electrons from the ligands fill all six bonding molecular orbitals, and the metal valence electrons occupy the $t_{2g}$ and $e_g^*$ orbitals. Ligands whose orbitals interact strongly with the metal orbitals are called strong-field ligands; with these, the split between the $t_... | {
"Header 1": "10.3.2 Orbital Splitting and Electron Spin",
"token_count": 1232,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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Determine the exchange energies for high-spin and low-spin $d^6$ ions in an octahedral complex.
In the high-spin complex, the electron spins are as shown on the right. The five \(\begin{align\*}
\text{ } \\
\text{ } \\
\text{ } \\
\text{ } \\
\text{ } \\
\text{ } \\
\text{ } \\
\text{ } \\
\text{ } \\
\text{ } \\
\... | {
"Header 1": "10.3.2 Orbital Splitting and Electron Spin",
"Header 3": "**EXAMPLE 10.1**",
"token_count": 1620,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
} |
$$\begin{array}{c|cccc}
& \uparrow 4 & \uparrow 5 \\
\hline
& \uparrow_1 \downarrow_1 & \uparrow_2 & \uparrow_3 \\
\hline
& & & \\
\hline
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
& & & \\
... | {
"Header 1": "10.3.2 Orbital Splitting and Electron Spin",
"Header 3": "**EXAMPLE 10.1**",
"token_count": 1641,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
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The difference between (1) the energy of the $t_{2g}/e_g$ electronic configuration resulting from the ligand field splitting and (2) the hypothetical energy of the $t_{2g}/e_g$ electronic configuration with all five orbitals degenerate and equally populated is called the ligand field stabilization energy (LFSE). Th... | {
"Header 1": "10.3.3 Ligand Field Stabilization Energy",
"token_count": 319,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
} |
Determine the LFSE for a $d^6$ ion for both high-spin and low-spin cases.
FIGURE 10.11 Splitting of Orbital Energies in a Ligand Field.
**Table 10.7** lists LFSE values for $\sigma$ -bonded octahedral complexes with 1-10 d electrons in both high- and low-spin arrangements. The fin... | {
"Header 1": "10.3.3 Ligand Field Stabilization Energy",
"Header 3": "**EXERCISE 10.7**",
"token_count": 2048,
"source_pdf": "datasets/websources/biochem/inorganic-chemistry-g-l-miessler-2014.pdf"
} |
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