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Figure 23.1
The transition elements (d block) and inner transition elements (f block) in the periodic table.
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Many transition metal compounds are colored and paramagnetic, whereas most main-group ionic compounds are colorless and diamagnetic.
The properties of transition metal compounds are related to the electron configuration of the metal ion.
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Figure 23.2
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The number of unpaired electrons increases in the first half of the 23-7 series and decreases in the second half, when pairing begins.
PROBLEM: Write condensed electron configurations for the following: (a) Zr; (b) V3+; (c) Mo3+. (Assume that elements in higher periods behave like those in Period 4.) PLAN: We locate the element in the periodic table and count its position in the respective transition series. These elements are in Periods 4 and 5, so the general electron configuration is [noble gas]ns2(n 1)dx. For the ions, we call that ns electrons are lost first.
SOLUTION:
(a) Zr is the second element in the 4d series: [Kr]5s24d2
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Electronegativity and ionization energies also increase relatively little across the transition metals of a particular period.
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Ionization energy values generally increase down a transition group, also running counter to the main group trend.
Density increases dramatically down a group since atomic volumes change little while atomic masses increase significiantly.
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Figure 23.4
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Elements in Groups 8B(8), 8B(9) and 8B(10) exhibit fewer oxidation states. The higher oxidation state is less common and never equal to the group number.
- The +2 oxidation state is common because the ns2 electrons are readily lost.
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Figure 23.5
+2 Mn2+
+6
+7 MnO4 The highest oxidation state for Mn equals its group number.
+5 VO43
+6
Cr2O72
+7 MnO4
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Table 23.2 Oxidation States and d-Orbital Occupancy of the Period 4 Transition Metals*
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Cr2+(aq) + 2e
Mn2+(aq) + 2e Fe2+(aq) + 2e Co2+(aq) + 2e Ni2+(aq) + 2e Cu2+(aq) + 2e Zn2+(aq) + 2e
Cr(s)
Mn(s) Fe(s) Co(s) Ni(s) Cu(s) Zn(s)
-0.91
-1.18 -0.44 -0.28 -0.25 0.34 -0.76
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Figure 23.6
potassium nickel(II) nitrate zinc sulfate titanium(IV) oxide sodium chromate ferricyanide hexahydrate heptahydrate
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IE1 increases down the group, so reactivity decreases. This trend is opposite to that seen in main-group elements.
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The atomic properties of the lanthanides vary little across the period, and their chemical properties are also very similar.
Most lanthanides have the ground-state electron configuation [Xe]6s24fx5d0. All actinides are radioactive, and have very similar physical and chemical properties. The +3 oxidation state is common for both lanthanides and actinides.
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PROBLEM: The alloy SmCo5 forms a permanent magnet because both samarium and cobalt have unpaired electrons. How many unpaired electrons are in Sm (Z = 62)? PLAN: We write the condensed electron configuration of Sm and then, using Hunds rule and the aufbau principle, place electrons into a partial orbital diagram and count the unpaired electrons. SOLUTION: Sm is the eighth element after Xe. Two electrons go into the 6s sublevel. In general, the 4f sublevel fills before the 5d, so the remaining six electrons go into the 4f sublevel. The condensed configuration of Sm is [Xe]6s24f6.
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Coordination Compounds
A coordination compound contains at least one complex ion, which consists of a central metal cation bonded to molecules and/or anions called ligands.
The complex ion is associated with counter ions of opposite charge.
The complex ion [Cr(NH3)6]3+ has a central Cr3+ ion bonded to six NH3 ligands. The complex ion behaves like a polyatomic ion in solution.
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Coordination Number
The coordination number is the number of ligand atoms bonded directly to the central metal ion. Coordination number is specific for a given metal ion in a particular oxidation state and compound.
- [Cr(NH3)6]3+ has a coordination number of 6.
The most common coordination number in complex ions is 6, but 2 and 4 are often seen.
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Figure 23.7
[Co(NH3)6]Cl3 dissolves in water. The six ligands remain bound to the complex ion.
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Square planar
[Ni(CN)4]2-, [PdCl4]2-,
[Pt(NH3)4]2+, [Cu(NH3)4]2+
Tetrahedral
Octahedral
The geometry of a given complex ion depends both on the coordination number and the metal ion.
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Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Ligands
The ligands of a complex ion are molecules or anions with one or more donor atoms. Each donor atom donates a lone pair of electrons to the metal ion to form a covalent bond.
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Chelates
Bidentate and polydentate ligands give rise to rings in the complex ion.
A complex ion containing this type of structure is called a chelate because the ligand seems to grab the metal ion like claws.
EDTA has six donor atoms and forms very stable complexes with metal ions.
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Carbonyl
Nitrosyl
CO
NO
Bromo
Iodo Hydroxo Cyano
BrIOHCN-
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Gold
Tin
Aurate
Stannate
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PROBLEM: (a) What is the systematic name of Na3[AlF6]? (b) What is the sytematic name of [Co(en)2Cl2]NO3? (c) What is the formula of tetraamminebromochloroplatinum(IV) chloride? (d) What is the formula of hexaamminecobalt(III) tetrachloroferrate(III)? PLAN: We use the rules for writing formulas and names of coordination compounds. SOLUTION: (a) The complex ion is [AlF6]3-. There are six (hexa-) F- ions (fluoro) as ligands. The complex ion is an anion, so the ending of the metal name must be changed to ate. Since Al has only one oxidation state, no Roman numerals are used. sodium hexafluoroaluminate
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Charge of complex ion = charge of metal ion + total charge of ligands = (4+) + [(4 x 0) + (1 x 1-) + (1 X 1-)] = +4 + (-2) = +2 or 2+
We will therefore need two Cl- counter ions to balance the charge on the complex ion. [Pt(NH3)4BrCl]Cl2
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Linkage isomers occur when the composition of the complex ion is the same but the ligand donor atom is different.
- Some ligands can bind to the metal through either of two donor atoms.
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The nitrite ion can bind either through the N atom or either one of the O atoms.
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Figure 23.9A
The cis and trans isomers of [Pt(NH3)2Cl2]. In the cis isomer, identical ligands are adjacent to each other, while in the trans isomer they are across from each other. The cis isomer (cisplatin) is an antitumor agent while the trans isomer has no antitumor effect.
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Figure 23.9B
The cis and trans isomers of [Co(NH3)4Cl2]+. Note the placement of the Cl- ligands (green spheres).
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Structure I and its mirror image, structure II, are optical isomers of cis-[Co(en)2Cl2]+.
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The trans isomer of [Co(en)2Cl2]+ does not have optical isomers. Structure I can be superimposed on its mirror image, structure II.
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Figure 23.11
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PLAN: We determine the geometry around each metal ion and the nature of the ligands. If there are different ligands that can be placed in different positions relative to each other, geometric (cis-trans) isomerism occurs. Then we see whether the mirror image of an isomer is superimposable on the original. If it is not, optical isomerism also occurs.
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These are geometric isomers; they do not have optical isomers since each compound is superimposable on its mirror image.
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This type of bond is called a coordinate covalent bond since both shared e- originate from one atom in the pair. In terms of valence bond theory, the filled orbital of the ligand overlaps with an empty orbital of the metal ion.
The VB model proposes that the geometry of the complex ion depends on the hybridization of the metal ion.
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Figure 23.12
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Figure 23.13
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Figure 23.14
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Figure 23.15
An artists wheel.
Each color has a complementary color; the one opposite it on the artists wheel. The color an object exhibits depends on the wavelengths of light that it absorbs.
An object will have a particular color because it reflects light of that color, or it absorbs light of the complementary color.
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The splitting of the d-orbitals depends on the relative orientation of the ligands.
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Figure 23.16
The ligands approach along the x, y and z axes. Two of the orbitals point directly at the ligands, while the other three point between them.
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Figure 23.17
The d orbitals split into two groups. The difference in energy between these groups is called the crystal field splitting energy, symbol .
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Figure 23.18
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Figure 23.19
Green and yellow light are absorbed while other wavelengths are transmitted. This gives a purple color.
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Figure 23.19
When the ion absorbs light, electrons can move from the lower t2g energy level to the higher eg level. The difference in energy between the levels () determines the wavelengths of light absorbed. The visible color is given by the combination of the wavelengths transmitted.
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Figure 23.20
[V(H2O)6]2+
[V(H2O)6]3+
[Cr(NH3)6]3+
[Cr(NH3)5Cl ]2+
Substitution of an NH3 ligand with a Cl- ligand affects the color of the complex ion.
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Figure 23.21
I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO WEAKER FIELD SMALLER D LONGER
STRONGER FIELD
LARGER D SHORTER
As increases, shorter wavelengths (higher energies) of light must be absorbed to excite electrons. For reference H2O is considered a weak-field ligand.
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PROBLEM: Rank the ions [Ti(H2O)6]3+, [Ti(NH3)6]3+, and [Ti(CN)6]3- in terms of and of the energy of visible light absorbed. PLAN: The formulas show that Ti has an oxidation state of +3 in all three ions. From Figure 23.21, we tank the ligands by crystal field strength: the stronger the ligand, the greater the splitting, and the higher the energy of light absorbed. SOLUTION: The ligand field strength is CN- > NH3 > H2O, so the relative size of and energy of light absorbed will be
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The number of unpaired e- will depend on the relative sizes of Epairing and .
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Figure 23.22
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Figure 23.23 Orbital occupancy for high-spin and low-spin octahedral complexes of d4 through d7 metal ions.
high spin: weak-field ligand low spin: strong-field ligand
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Sample Problem 23.6 Identifying High-Spin or Low-Spin Complex Ions PROBLEM: Iron (II) forms a complex in hemoglobin. For each of the two octahedral complex ions [Fe(H2O)6]2+ and [Fe(CN)6]4, draw an energy diagram showing orbital splitting, predict the number of unpaired electrons, and identify the ion as low spin or high spin.
PLAN: Fe2+ electron configuration shows the number of d electrons, and the spectrochemical series shows the relative ligand strengths. We draw energy diagrams and separate the t2g and eg orbital sets more for the strong-field ligand. Then we add electrons, noting that a weak-field ligand gives the maximum number of unpaired electrons and a high-spin complex, whereas the strong-field ligand will give the minimum number of unpaired electrons and a low-spin complex.
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Potential energy
eg t2g
t2g
[Fe(H2O)6]2+ high-spin
[Fe(CN)6]4low-spin
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The splitting of d-orbital energies is less in a tetrahedral than an octahedral complex, and the relative d-orbital energies are reversed. Only high-spin tetrahedral complexes are known because is small.
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Square planar complexes are low-spin and usually diamagnetic because the four pairs of d electrons fill the four lowest-energy orbitals.
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Chemical Connections Figure B23.1 Hemoglobin and the octahedral complex in heme.
Hemoglobin consists of four protein chains, each with a bound heme. In oxyhemoglobin (B), the octahedral complex in heme has an O2 molecule as the sixth ligand for iron(II).
(Illustration by Irving Geis. Rights owned by Howard Hughes Medical Institute. Not to be used without permission.)
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Chemical Connections Figure B23.2 The tetrahedral Zn2+ complex in carbonic anhydrase.
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