M23 Wils2248 14 Se C23

Transition Metals
23 and Coordination
Chemistry
Visualizing Concepts
23.1 Analyze/Plan. Given graphs of three properties moving across the fourth period of the
chart, match each graph to the atomic property it represents. Solve.
Graph (a) is the trend in maximum oxidation state. This value corresponds to the
maximum number of (4s + 3d) electrons that can be removed from a neutral atom. It
increases up to a maximum of +7 for Mn, then decreases. The decrease is partly because
of an increase in the attraction of 3d electrons for the nucleus as Zeff increases.
Graph (b) is the trend in effective nuclear charge, Zeff. Moving from left to right in a
period, Zeff increases because the increase in Z is not offset by a significant increase in
shielding.
Graph (c) is the trend in radius. Increasing Zeff leads to decreasing atomic radius.
23.2 Analyze. Given the formula of a coordination compound, draw the structure, determine
the coordination number, coordination geometry, oxidation state of the metal, and
number of unpaired electrons.
Plan. From the formula, determine the identity of the ligands and the number of
coordination sites they occupy. From the total coordination number, decide on a likely
geometry. Use ligand and overall complex charges to calculate the oxidation number of
the metal. Refer to the d‐orbital energy level diagram that corresponds to the structure
of the compound and the field strength of the ligands to determine the number of
unpaired electrons.
Solve. The ligands are 2 NH3, one coordination site each, and C2O42−, oxalate dianion,
two coordination sites, for a coordination number of 4. This coordination number has
two possible geometries, tetrahedral and square planar. Pt is one of the metals known
to adopt square planar geometry when CN = 4.
(a) Coordination number is 4

(b) Coordination geometry is square planar
(c) The oxidation state of Pt is +2. Pt(C2O4)(NH3)2 is a neutral compound, the NH3
ligand is neutral, and the C2O4 ligands has the charge –2, so the oxidation state of
Pt must be +2, Pt(II).
(d) There are no unpaired electrons. Square planar d8 complexes are usually low
spin, especially with heavier metals like Pt.
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Copyright © 2018 Pearson Education Ltd.
23 Transition Metals and Solutions to Exercises
Coordination Chemistry
23.3 Analyze. Given a ball-and-stick figure of a ligand, write the Lewis structure and answer
questions about the ligand.
Plan. Assume that each atom in the Lewis structure obeys the octet rule. Complete each
octet with unshared electron pairs or multiple bonds, depending on the bond angles in
the ball-and-stick model. Black = C, blue = N, red = O, gray = H.
There is a second resonance structure with the double bond drawn to the other O atom.
Check. Write the molecular formula, count the valence electron pairs and see if it
matches your structure. [C 4H 9N 2O 2] – (16 + 9 + 10 + 12 + 1) = 48 valence e –, 24 e – pair
Our Lewis structure also has 24 e – pairs.
(a) Donor atoms have unshared electron pairs. The potential donors in this structure
are the two N and two O atoms.
The ligand is polydentate. If bound to a single metal center, it is likely to be

tridentate. Even though there are four possible donor atoms, the structure would
be strained if all four were bound to one metal center. It is likely that only one of
the two O atoms binds to the same metal as the two N atoms. If it is bound to
more than one metal, it could use all four donor atoms.
(b) An octahedral complex has 6 coordination sites. A single ligand has 3 likely
donors, so two ligands are needed. From a steric perspective, the likely donors
would be the 2 N atoms and 1 of the carbonyl oxygen atoms. The chelate bite of a
carboxyl group is relatively small and would require an O — M — O angle of less
than 90.
23.4 Analyze/Plan. Given the molecular formula, name the compound. Use the ball-and-stick
structures to decide the number of geometric isomers for each molecular geometry.
Consider the d-electron configuration of platinum(II) and the appropriate crystal field
splitting diagrams (Figures 23.33 and 23.34) to determine magnetic properties for the two
molecular geometries. Solve.
(a) Diaminodichloroplatinum(II). If the geometry is square planar, the prefix cis-

would be added.
(b) No, the tetrahedral molecule would not have a geometric isomer.
(c) The tetrahedral molecule would be paramagnetic. Platinum(II) is a d8 transition

metal ion. In a tetrahedral crystal field (Figure 23.33 and Sample Exercise 23.8),
there would be two unpaired d-electrons and the molecule would be
paramagnetic.
(d) Yes, the square planar molecule would have a geometric isomer, the trans isomer.
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(e) The square planar molecule would be diamagnetic. A d8 transition metal ion in a
square planar crystal field (Figure 23.34 and Sample Exercise 23.8) has no
unpaired electrons.
(f) Yes, you would be able to distinguish the two geometries by determining the
number of geometric isomers. The square planar geometry has two possible
isomers, cis and trans, while the tetrahedral geometry has one unique structure.
(g) Yes, you would be able to distinguish the two geometries by measuring the
molecule’s response to a magnetic field. The tetrahedral molecule is attracted to a
magnetic field, while the square planar molecule is not.
23.5 Analyze. Given 5 structures, visualize which are identical to (1) and which are geometric
isomers of (1).
Plan. There are two possible ways to arrange MA 3X 3. The first has bond angles of 90
between all similar ligands; this is structure (1). The second has one 180 angle between
similar ligands. Visualize which description fits each of the five structures.
Solve. (1) has all 90 angles between similar ligands.

(2) has a 180 angle between similar ligands (see the blue ligands in the
equatorial plane of the octahedron)
(3) has all 90 angles between similar ligands
(4) has all 90 angles between similar ligands
(5) has a 180 angle between similar ligands (see the blue axial ligands)
Structures (3) and (4) are identical to (1); (2) and (5) are geometric isomers.
23.6 Analyze. Given four structures, decide which are chiral.
Plan. Chiral molecules have nonsuperimposable mirror images. Draw the mirror image
of each molecule and visualize whether it can be rotated into the original molecule. If
so, the complex is not chiral. If the original orientation cannot be regenerated by
rotation, the complex is chiral. Solve.
The two orientations are not superimposable and molecule (1) is chiral.
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The two orientations are superimposable. Rotate the right-most structure 90
counterclockwise about the B-M-B axis to align the G’s; the bidentate ligands then also
overlap. Molecule (2) is not chiral.
23.7 Analyze. Given the visible colors of two solutions, determine the colors of light absorbed
by each solution.
Plan. Apparent color is transmitted or reflected light, absorbed color is basically the
complement of apparent color. Use the color wheel in Figure 23.25 to obtain the
complementary absorbed color for the solutions.
Solve. Moving from left to right, the solutions appear blue-green (cyan), yellow, green,
and red. The solutions absorb red-orange, violet, red, and green.
23.8 Analyze. Fit the crystal field splitting diagram to the complex description in each part.
Plan. Determine the number of d-electrons in each transition metal. On the splitting
diagrams match the d-orbital splitting patterns to complex geometry and electron
pairing to the definition of high-spin and low-spin.
Solve. Octahedral complexes have the 3 lower, 2 higher splitting pattern, whereas
tetrahedral complexes have the opposite 2 lower, 3 higher pattern. Low spin complexes
favor electron pairing because of large d-orbital splitting. High-spin complexes have
maximum occupancy because of small orbital splitting.
(a) Fe3+, 5 d-electrons; weak field: spins unpaired; octahedral: 3 lower, 2 higher
d-splitting  diagram (4)
(b) Fe 3+, 5 d-electrons; strong field: spins paired; octahedral: 3 lower, 2 higher
d-splitting  diagram (1)
(c) Fe 3+, 5 d-electrons; tetrahedral: 2 lower, 3 higher d-splitting  diagram (3)
(d) Ni 2+, 8 d-electrons; tetrahedral: 2 lower, 3 higher d-splitting  diagram (2)
Check. Diagram (2) was the remaining choice for (d) and it fits the description.
23.9 Analyze/Plan. Given the linear diagram and axial labels, answer the questions and
predict crystal field splitting. Orbitals with lobes nearest ligand charges (or partial
charges) will be highest in energy; orbitals with lobes away from charges are lowest in
energy.
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Solve. Diagram (c) is the best choice. The d z2 orbital has lobes nearest the charges and
is at the highest energy. The d x2  y2 and d xy orbitals have lobes in the xy-plane
farthest from the charges and are lowest in energy. The d xz and d yz orbitals point
between the respective axes and are intermediate in energy.
d z2
d xz, d yz
d xz, d x2  y2
23.10 Analyze. Given the colors of two low spin Co(III) complexes, determine which complex
contains the stronger field ligand.
Plan. We can make this direct comparison because both solutions contain low spin d6
ions. A solution that appears one color absorbs visible light of the complementary color.
Use the color wheel in Figure 23.25 to decide which color and approximate wavelength
of visible light is absorbed by the two solutions. The stronger‐field ligand causes a
larger d‐orbital splitting and absorbs light with the shorter wavelength.
Solve. The orange solution absorbs blue light in the 430 to 490 nm range. The yellow
solution absorbs violet light in the 400 to 430 nm range. The complex that produces the
yellow solution has the larger d‐orbital splitting and the stronger‐field ligand.
The Transition Metals (Section 23.1)

23.11 Trend (c). The lanthanide contraction is the name given to the decrease in atomic size
because of the build-up in effective nuclear charge as we move through the lanthanides
(elements 57–71) and beyond them. This effect offsets the expected increase in atomic
size going from period 5 to period 6 transition elements.
23.12 Trend (b) explains the peak in maximum oxidation state of the transition-metal elements
near groups 7 and 8. As effective nuclear charge increases, d-electrons are more strongly
attracted to the nucleus and more difficult to remove from the atom.
23.13 (a) Cu2+, [Ar]3d9 (b) Cu+, [Ar]3d10 (c) V5+, [Ar] (d) Mn2+, [Ar]3d5
23.14 Refer to Figure 23.5. Among the period 4 transition metals, only Sc and Zn do not have at
least one oxidation state with partially filled 3d orbitals. Sc3+ has zero 3d electrons and
Zn2+ has ten 3d electrons. In Sc3+ the 3d orbitals are unoccupied; in Zn2+ the 3d orbitals are
filled.
23.15 (a) Sc2+, [Ar]3d1 (b) Mo2+, [Kr]4d4 (c) Rh3+, [Kr]4d6 (d) Fe3+, [Ar]3d5
23.16 (a) Ru3+, [Kr]4d5; 5 valence d‐electrons

(b) Pd2+, [Kr]3d8; 8 valence d‐electrons
(c) Ti2+, [Ar]3d2; 2 valence d‐electrons
(d) W6+, [Xe]4f14; 0 valence d‐electrons
688
23.17 Analyze/Plan. Consider the definitions of paramagnetic and diamagnetic. Solve.
The unpaired electrons in a paramagnetic substance cause it to be weakly attracted into
a magnetic field. (A diamagnetic material, where all electrons are paired, is very weakly
repelled by a magnetic field.)
23.18 Antiferromagnetic materials cannot be used to make permanent magnets. In an

antiferromagnetic material, coupled spins are aligned in opposite directions and the
opposing spins exactly cancel.
23.19 Analyze/Plan. Consider the orientation of spins in various types of magnetic materials as
shown in Figure 23.6.
The diagram shows a material with misaligned spins that become aligned in the
direction of an applied magnetic field. This is a paramagnetic material.
23.20 (a) Fe2O3 has all Fe atoms in the +3 oxidation state, whereas Fe3O4 contains Fe atoms
in both the +2 and +3 states. Each Fe3O4 formula unit has one Fe(II) and two
Fe(III).
(b) In an antiferromagnetic material, spins on coupled atoms are oppositely aligned,

producing a net spin of zero. This is only possible for Fe2O3, where all Fe atoms have
the same oxidation state, d-electron configuration and number of unpaired
electrons. In Fe3O4, Fe(II) and Fe(III) atoms have different d-electron configurations
and different numbers of unpaired electrons. Assuming an Fe(II) is coupled to an
Fe(III), even if spins on coupled centers are oppositely aligned, their spins do not
fully cancel and the material is ferromagnetic.
Transition-Metal Complexes (Section 23.2)

23.21 (a) Primary valence. In Werner’s theory, primary valence is the charge of the metal
cation at the center of the complex. “Oxidation state” is a broader term than
“ionic charge,” but Werner’s complexes contain metal ions where cation charge
and oxidation state are equal.
(b) Coordination number. In Werner’s theory, secondary valence is the number of
atoms bound or coordinated to the central metal ion.
(c) NH3 can serve as a ligand because it has an unshared electron pair, whereas BH3
does not. Ligands act as a Lewis base in metal-ligand interactions. As such, they
must possess at least one unshared electron pair. BH3, with fewer than 8 electrons
about B, has no unshared electron pair and cannot act as a ligand. In fact, BH3 acts
as a Lewis acid, an electron pair acceptor, because it is electron-deficient.
23.22 (a) Negatively charged ions are more likely to act as ligands, to take advantage of the
electrostatic attraction between a positively charged metal cation and a negatively
charged ligand.
(b) Polar molecules are more likely to act as ligands to take advantage of ion-dipole
interactions between a positively charged metal cation and a polar ligand.
689
23.23 Analyze/Plan. Follow the logic in Sample Exercises 23.1 and 23.2. Solve.
(a) This compound is electrically neutral, and the NH 3 ligands carry no charge, so
the charge on Ni must balance the –2 charge of the 2 Br – ions. The charge and
oxidation state of Ni is +2.
(b) Because there are 6 NH 3 molecules in the complex, the likely coordination
number is 6. In some cases Br – acts as a ligand, so the coordination number could
be other than 6.
(c) Assuming that the 6 NH 3 molecules are the ligands, 2 Br – ions are not
coordinated to the Ni 2+, so 2 mol AgBr(s) will precipitate.
23.24 (a) [Cr(H 2O) 6]3+

(b) Three. Because the Cl– ions are not in the coordination sphere, all 3 anions react
with Ag+ to form 3 moles of AgCl(s).
(c) If the empirical formula of the compound is CrCl3 and Cr3+ has a coordination
number of six, some or all of the Cl– ions must be shared by more than one Cr3+ ion.
This produces a network solid that is very difficult to dissolve or break down.
23.25 Analyze/Plan. Count the number of donor atoms in each complex, taking the identity of
polydentate ligands into account. Follow the logic in Sample Exercise 23.2 to obtain
oxidation numbers of the metals.
(a) Coordination number = 6, oxidation number = +2
(b) 4, +7
(c) 4, +2
(d) 6, +3
(e) 4, +1
(f) 4, +2
23.26 (a) Coordination number = 4, oxidation number = +2
(b) 4, +2
(c) 4, +8
(d) 6, +2
(e) 6, +3
(f) 4, +2
Common Ligands in Coordination Chemistry (Section 23.3)

23.27 (a) CH3CH2NH2, 20 e –, 10 e – pr
monodentate ligand, only N atom has a nonbonded pair of electrons
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(b) P(CH3)3, 26 e –, 13 e – pr
monodentate ligand, only P atom has a nonbonded pair of electrons

(c) CO32−, 24 e –, 12 e – pr
either monodentate or bidentate

[All three O atoms are possible bonding sites, but it is not geometrically possible
for all three O atoms to be bound to the same metal ion.]
(d) C2H6 , 14 e –, 7 e – pr
unlikely to act as a ligand, no nonbonded pairs of electrons
23.28 (a) 2 coordination sites, 2 O donor atoms
(b) 2 coordination sites, 2 N donor atoms

(c) 3 coordination sites, 3N donor atoms
(d) 2 coordination sites, 2 O donor atoms
(e) 3 coordination sites, 3 O donor atoms
23.29 Analyze/Plan. Given the formula of a coordination compound, determine the number of
coordination sites occupied by the polydentate ligand. The coordination number of the
complexes is probably 4 or 6. Note the number of monodentate ligands and determine
the number of coordination sites occupied by the polydentate ligands. Solve.
(a) Ethylenediaminetetraacetate, EDTA is hexadentate. The complex is 6‐coordinate
and the EDTA occupies all 6 coordination sites.
(b) Oxalate, C2O42–, is bidentate. The complex is 4‐coordinate, there are 2
monodentate H2O ligands, so oxalate occupies 2 coordination sites.
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(c) Ethylenediamine, en, is bidentate. The complex is 6‐coordinate. The 4
monodentate NH3 ligands occupy 4 coordination sites and the en ligand occupies
the remaining 2 coordination sites.
(d) ortho‐Phenanthroline, o‐phen, is bidentate. The complex is 6‐coordinate, there are
4 monodentate CN ligands, so o‐phen occupies 2 sites.
23.30 (a) 6 (b) 6 (c) 4 (d) 6
23.31 Analyze/Plan. Anions and polar molecules (with nonbonded electron pairs) are most
likely to act as ligands in a metal complex (Solution 23.22). Solve.
(a) CO32−, anion
(b) H2O, polar molecular with nonbonded electron pair
(c) PH3, polar molecule with a nonbonded electron pair
23.32 (a) Pyridine is a monodentate ligand because it has one N donor atom and therefore
occupies one coordination site in a metal complex.
(b) K for this reaction will be smaller than one. Two free pyridine molecules are
replaced by one free bipy molecule. There are more moles of particles in the
reactants than products, so S is predicted to be negative. Processes with a net
decrease in entropy are usually nonspontaneous, have positive G, and values of
K less than one. This equilibrium is likely to be spontaneous in the reverse
direction.
23.33 True. The ligand shown in the figure can act as a bidentate ligand for a single metal
center. The CH2 groups between the two oxygen atoms are sp3 hybridized and allow
some bending in the molecule so that the two oxygen atoms can approach one single
metal center simultaneously for chelation.
23.34 (a) The complex shown in the exercise has tetrahedral geometry about the silver.
(b) The ligands are neutral molecules and the metal is Ag(I), so the complex will
have a 1+ charge.
(c) Yes, one nitrate ion, NO 3–, will be present in the crystal to provide charge balance
for the complex cation.
(d) [Ag(o-phen)2]NO 3
( e) bis(ortho-phenanthroline)silver(I) nitrate
Nomenclature and Isomerism in Coordination Chemistry (Section 23.4)

23.35 Analyze/Plan. Given the name of a coordination compound, write the chemical formula.
Refer to Tables 23.4 and 23.5 to find ligand formulas. Place the metal complex (metal ion
+ ligands) inside square brackets and the counterion (if there is one) outside the
brackets. Solve.
(a) [Cr(NH3)3(H2O)3](NO3)3 (b) [Pt(en)Cl2] (c) [Fe(CO)5]
(d) (NH4)2[Co(C2O4)2(H2O)2] (e) [Co(bipy)3]2(SO4)3
692
23.36 (a) [Fe(NH3)6](NO3)2 (b) [CrBr2(H2O)4]ClO4
(c) (NH3)2[PdCl6] (d) [Ni(NH3)2(C2O4)]
(e) [Mo(NH3)6]2[CuCl4]3
23.37 Analyze/Plan. Follow the logic in Sample Exercise 23.3, paying attention to naming rules
in Section 23.4. Solve.
(a) diamminesilver(I) nitrate
(b) mercury(II) tetrathiocyanatocobaltate(II)
(c) trichlorotris(triphenylphosphine)ruthenium(III)
(d) pentaamminecarbonatocobalt(III) sulphate
23.38 (a) sodium pentacyanonitrosylferrate(II)
(b) pentaammineoxocobalt(III) bromide
(c) sodium tetrabromonickelate(II)
(d) hexaaquarhodium(III) dicyanoargentate(I)
23.39 Analyze/Plan. Consider the coordination number and geometry of each of the
complexes, along with the definitions of the various types of isomerism. Use this
information to decide which of the complexes could exhibit isomerism of the specified
type. Solve.
Complex 1 has a coordination number of 6 and octahedral geometry about the metal.
There are 4 monodentate ligands of one kind and two of another.
Complex 2 has a coordination number of 4 and square planar geometry. There are two
monodentate ligands of one kind and two of another.
There are 2 bidentate ligands and two monodentate ligands.
(a) Complexes 1, 2, and 3 can have geometric isomers. These are different
arrangements of the same set of ligands. All three complexes have cis-trans
isomers, where a pair of ligands is either opposite or adjacent to each other.
(b) Only complex 2 can have linkage isomers. Nitrite ion, NO 2–, can coordinate
through either N or O. It is the only ligand in the three complexes that has this
ability.
(c) Only the cis geometric isomer of complex 3 can have optical isomers. These are
isomers, with the same arrangement of bonds, that are mirror images of each
other and cannot be superimposed.
(d) Only complex 1 can have coordination sphere isomers. This is where an anion
can either be a ligand or a counterion. Complex 1 is the only example with a
counterion that can also be a ligand.
693
23.40 Complex 1 has a coordination number of 6 and octahedral geometry about the metal.
There are 5 monodentate ligands of one kind and one of another.
Complex 2 has a coordination number of 6 and octahedral geometry. There are three
monodentate ligands of one kind and three of another.
There are 5 monodentate ligands of one kind and one of another.
(a) Only complex 2 has geometric isomers. It is the only complex with different
possible arrangements of the same ligands. There is only one unique way to
arrange 5 ligands of one kind and one of another, as in complex 1 and 3.
(b) Only complex 1 can have linkage isomers. Thiocyanate ion, SCN–, can coordinate
through either N or S. It is the only ligand in the three complexes that has this
ability.
(c) None of the complexes has optical isomers. None of the complexes has bidentate
ligands, which are usually present in optically active octahedral complexes.
(d) Only complex 3 can have coordination sphere isomers. This is where an anion
can either be a ligand or a counterion. Complex 3 is the only example with anions
that are not specifically written as ligands.
23.41 Yes. A tetrahedral complex of the form MA 2B 2 would have neither structural isomers
nor stereoisomers. For a tetrahedral complex, no differences in connectivity are possible
for a single central atom, so the terms cis and trans do not apply. No optical isomers
with tetrahedral geometry are possible because M is not bound to four different groups.
The complex must be square planar with cis and trans geometric isomers.
23.42 Two geometric isomers are possible for an octahedral MA2B4 complex, trans and cis (see
below). There are no optical isomers for the for both cis and trans form as the mirror
images of these molecules are superimposable.
23.43 Analyze/Plan. Follow the logic in Sample Exercise 23.4 and 23.5. Solve.
(a) No geometric isomers (b) Two geometric isomers, cis and trans
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(c) Three geometric isomers: cis and trans; the cis isomer has enantiomers
(The three isomeric complex ions in part (c) each have a 1+ charge.)
23.44 (a) Two geometric isomers (enantiomers)
N N
N N
N N
Rh Rh
N N N N
N N
enantiomers
optical isomers
(b) Two geometric isomers. In one, the three ammonia ligands are all cis to each
other; in the other, one pair of ammonia ligands are trans.
NH3 NH3
N NH3 N NH3
Co Co
N NH3 N Br
Br NH3
(c) No geometric isomers

CN
HN Pd CN
NH
695
23.45 Analyze/Plan. Consider the geometry and arrangement of ligands in each complex.
Decide whether the structure has a nonsuperimposable mirror image. Solve.
(a) Not chiral. The tetrahedral Zn2+ is not bonded to four different ligands.
(b) Not chiral. One mirror image can be superimposed on the other. [See similar
trans structure in Solution 23.43 (c)]
(c) Chiral, has an optical isomer. [See similar cis structures in Solution 23.43 (c)]
23.46 (a) Not chiral. A square planar complex cannot be chiral.

(b) Not chiral. One mirror image can be superimposed on the other.
(c) Chiral. One mirror image cannot be superimposed on the other.
Color and Magnetism in Coordination Chemistry; Crystal-Field Theory

(Sections 23.5 and 23.6)
23.47 (a) Visible light with a wavelength of 610 nm is orange. If the complex absorbs
orange light, it will appear blue.
(b) E(J/photon) = h = hc/.
6.626  1034 J-s 2.998  108 m 1nm
E    3.257  1019  3.26  1019 J
610 nm s 1 109 m
(c) Change J/photon to kJ/mol.
3.259  1019 J 1kJ 6.022  1023 photons
   196 kJ/m ol
photon 1000 J m ol
23.48 (a) E(J/photon) = hc/.  = hc/E.

6.626  1034 J-s 2.998  108 m 1nm
    440.46  440 nm
4.51  1019 J/photon s 1  109 m
(b) If the complex absorbs only 441 nm visible light, it absorbs violet and appears
yellow.
23.49 Analyze/Plan. Given the formula of a coordination complex, determine the oxidation
state and electron configuration of the central metal ion. If necessary, use a d‐orbital
energy level diagram appropriate for the geometry of the complex to decide if the metal
ion has unpaired electrons. If so, it is paramagnetic.
(a) Co3+, [Ar]3d6. Since the complex is low spin, there are no unpaired electrons, so
the complex is diamagnetic.
(b) W3+, [Xe]4f14d3. There are 3 d‐electrons, so the complex is paramagnetic.
(c) V3+, [Ar]3d2. There are 2 d‐electrons, so the complex is paramagnetic. The
complex is octahedral, but the two electrons would be unpaired in any of the d‐
orbital energy level diagrams.
(d) Rh3+, [Kr]4d6. The complex is diamagnetic. With a period 5 (or 6) metal center, the
complex is usually low spin. The geometry is octahedral and there are no
unpaired electrons.
696
23.50 (a) Zn2+, [Ar]3d10. The complex is diamagnetic.
(b) Mn3+, [Ar]3d4. It is a high spin complex with d‐electrons, so the complex is
paramagnetic.
(c) Os8+, [Xe]4f14. There are 0 d‐electrons, so the complex is diamagnetic.
(d) Pt2+, [Xe]4f145d8. The complex is diamagnetic. This complex adopts square planar
geometry. With a period 6 metal center, the complex is usually low spin and has
no unpaired electrons.
23.51 An electron in a d orbital with lobes that point directly at the ligands will have higher
energy than an electron in a d orbital with lobes that do not point directly at the ligands.
23.52 (a) The six ligands in an octahedral arrangement are oriented along the x, y, and z
axes of the metal. The d xy, d xz, and d yz metal orbitals point between the x, y, and
z axes, and also between the ligands in this arrangement.
(b) The four ligands in a tetrahedral arrangement are oriented between the x, y, and
z axes of the metal. The d orbitals along the axes, d x2  y2 and d z2 , point between
the ligands.
23.53 (a)
(b) The magnitude of  and the energy of the d-d transition for a d 1 complex are
equal.
6.626  1034 J-s 2.998  108 m 1nm 1kJ 6.022  1023 photons
(c)   9
 
545 nm s 1 10 m 1000 J m ol
= 220 kJ/mol
6.626  1034 J-s 2.998  108 m /s

23.54 (a)  E  hc/    3.973  1019
500  109 m photon
 3.97  1019 J/photon
6.022  1023 photons 1kJ
  3.973  1019 J/photon    239.25
1m ol 1000 J
 239 kJ/m ol
(b) NH 3 is higher than H 2O in the spectrochemical series, an ordering of ligands
according to their ability to increase the energy gap, . If H 2O is replaced by NH 3
in the complex, the magnitude of  would increase because NH 3 is higher in the
spectrochemical series and creates a stronger ligand field.
697
23.55 Analyze/Plan. Determine the oxidation state of the copper ions in each mineral from their
molecular formulas. Write the appropriate electron configuration(s). Consider the
relationship between d-orbital electron configuration, the color of a complex, the
wavelength of absorbed light, and the magnitude of the crystal field splitting . Solve.
(a) Both minerals contain Cu2+ ions. The electron configuration of Cu2+ is [Ar]3d9.
(b) Azurite will probably have the larger ∆. Malachite appears green and absorbs red.
Azurite appears blue and absorbs orange. Orange light has a wavelength range of
580 to 650 nm, whereas red light has wavelengths between 650 and 750 nm. The
shorter wavelengths of the orange light absorbed by azurite correspond to higher-
energy electron transitions and larger ∆ values.
23.56 (a) Red. The [Ni(bipy)2 ]2+ ion absorbs 520 nm green light and appears as the
complementary color, red. This fits the absorbed wavelength vs observed color
trend shown in Figure 23.30.
(b) The shorter the wavelength of light absorbed, the greater the value of , and the
stronger the ligand field. The order of increasing ligand field strength is the order
of decreasing wavelength absorbed.
H2O < NH3 < en < bipy
23.57 Analyze/Plan. Determine the charge on the metal ion, subtract it from the row number
(3‐12) of the transition metal, and the remainder is the number of d‐electrons. Solve.
(a) Pt3+, d8 (b) Cu2+, d9 (c) Os3+, d5
(d) Cr2+, d4 (e) Cd2+, d10
23.58 (a) Cr3+, d3 (b) Zr2+, d2 (c) Cu2+, d9

(d) Ni2+, d8 (e) Fe3+, d5
23.59 Yes. A weak-field ligand leads to a small ∆ value and a small d-orbital splitting energy.
If the splitting energy of a complex is smaller than the energy required to pair electrons
in an orbital, the complex is high-spin.
23.60 Octahedral. In an octahedral crystal field, there are more ligand point charges to
interact with d orbitals on the metal. And, the point charges point directly at the metal d
orbitals so the interaction is greater.
23.61 Analyze/Plan. Follow the logic in Sample Exercise 23.7. Solve.

(a) Mn: [Ar]4s 23d 5 (b) Ru: [Kr]5s 14d 7 (c) Rh: [Kr]5s 14d 8
Mn 2+: [Ar]3d 5 Ru 2+: [Kr]4d 6 Rh 2+: [Kr]4d 7
1 unpaired electron 0 unpaired electrons 1 unpaired electron
698
23.62 (a) Fe: [Ar]4s 23d 6 (b) Mo: [Kr]5s 14d 5 (c) Co: [Ar]4s 23d 7
Fe3+: [Ar]3d 5 Mo 3+: [Kr]4d 3 Co 3+: [Ar]3d 6
5 unpaired electrons 3 unpaired electrons 4 unpaired electrons
23.63 Analyze/Plan. All complexes in this exercise are six-coordinate octahedral. Use the
definitions of high-spin and low-spin along with the orbital diagram from Sample
Exercise 23.7 to place electrons for the various complexes. Solve.
d 5, low spin d3 d8
23.64
23.65 Analyze/Plan. Follow the ideas but reverse the logic in Sample Exercise 23.7. Solve.
699
23.66
Both complexes contain Fe 3+, a d 5 ion. CN –, a strong field ligand, produces such a large
 that the splitting energy is greater than the pairing energy, and the complex is low
spin. NCS – produces a smaller , so it is energetically favorable for d-electrons to be
unpaired in the higher energy d-orbitals. NCS – is a much weaker-field ligand than CN –.
It is probably weaker than NH 3 and near H 2O in the spectrochemical series.
Additional Exercises
23.67 The paper clip must contain a significant amount of Ni, a ferromagnetic metal. At
ambient temperature, the paper clip is below its Curie temperature, behaves
ferromagnetically, and is strongly attracted to the permanent magnet. The lighter heats
the left paperclip above its Curie temperature (354 oC), and it switches from from
ferromagnetic to paramagnetic behavior. That is, below its Curie temperature, the spins
of the unpaired electrons in Ni are perfectly aligned and the clip is strongly attracted to
the permanent magnet. Above the Curie temperature, the unpaired spins become
randomly aligned, and the paper clip loses most of its attraction for the permanent
magnet.
23.68 We expect radii in a group to increase moving down the periodic table as principle
quantum number increases. However, the nuclear build-up associated with filling of
the 4f subshell at the beginning of period 6 counteracts this trend. The increased nuclear
charge for transition metals of period 6 means that the valence electrons experience a
Zeff large enough to offset the increase in principle quantum number. The increased Zeff
causes the radii of the metals in group 6 to be smaller than expected, and period 5 and
6 metals in the same group to have very similar radii. This phenomenon is called the
lanthanide contraction.
23.69 [Pt(NH 3) 6]Cl 4; [Pt(NH 3) 4Cl 2]Cl 2; [Pt(NH 3) 3Cl 3]Cl; [Pt(NH 3) 2Cl 4]; K[Pt(NH 3)Cl 5]
23.70
2 Cl– 3 Cl–
700
23.71 (a) (b)
square planar
tetrahedral
(c) (d)
octahedral octehedral
(a) cis‐bromochlorodinitroplatinate(II) ion

(b) benzenetricarbonvlmanganese(I) ion
(c) cis‐diaquatetrachlorochromate(III) ion
(d) trans‐chlorobis(ethylenediamine)hydroxocobalt(III) ion
23.72 No. Since complex d is a trans‐isomer, the mirror images are superimposable.
23.73 (a) Valence electrons: 2P + 6C + 16H = 10 + 24 + 16 = 50 e –, 25 e – pr
Both dmpe and en are bidentate ligands. The dmpe ligand binds through P,
whereas en binds through N. Phosphorus is less electronegative than N, so dmpe
is a stronger electron pair donor and Lewis base than en. Dmpe creates a stronger
ligand field and is higher on the spectrochemical series.
Structurally, P has a larger covalent radius than N, so M–P bonds are longer than
M–N bonds. This is convenient because the two –CH3 groups on each
P atom in dmpe create more steric hindrance (bumping with adjacent atoms)
than the H atoms on N in en.
(b) CO and dmpe are neutral, 2 CN– = 2–, 2 Na+ = 2+. The ion charges balance, so the
oxidation state of Mo is zero.
701
(c) The symbol P P represents the bidentate dmpe ligand.
CN CO
P CO P CN
Mo Mo
P CO P CN
CN CO
CN CN
P CN NC P
Mo Mo
P CO OC P
CO CO
optical isomers
23.74 The trans isomer is not observed. In a square planar complex such as [Pt(en)Cl2], if one pair
of ligands is trans, the remaining two coordination sites are also trans to each other.
Ethylenediamine is a relatively short bidentate ligand that cannot occupy trans
coordination sites, so the trans isomer is unknown.
23.75 We will represent the end of the bidentate ligand containing the CF 3 group by a shaded
oval, the other end by an open oval:
23.76 (a) Iron. Hemoglobin is the iron-containing protein that transports O 2 in human
blood.
(b) Magnesium. Chlorophylls are magnesium-containing porphyrins in plants. They

are the key components in the conversion of solar energy into chemical energy
that can be used by living organisms.
(c) Iron. Siderophores are iron-binding compounds or ligands produced by a
microorganism. They compete on a molecular level for iron in the medium
outside the organism and carry needed iron into the cells of the organism.
(d) Copper. Hemocyanine is a copper-containing protein responsible for oxygen
transport in the blue blood of certain marine animals.
23.77 (a) Zero. The CO ligand is a neutral molecule and the charge on the complex is zero,
so nickel must be present as Ni(0).
(b) The electron configuration of a Ni atom in the absence of a ligand field is [Ar]4s23d8.
A tetrahedral complex with 8 d-electrons would have two unpaired electrons and be
paramagnetic. Because the compound is diamagnetic, the Ni atom must have 10 d-
electrons. The electron configuration of Ni in the complex is [Ar]3d10.
(c) tetracarbonylnickel(0)
702
23.78 (a) pentacarbonyliron(0)
(b) Because CO is a neutral molecule, the oxidation state of iron must be zero.
(c) [Fe(CO)4CN]– has two geometric isomers. In a trigonal bipyramid, the axial and
equatorial positions are not equivalent and not superimposable. One isomer has
CN in an axial position and the other has it in an equatorial position.
23.79 (b) a computer keyboard,

(c) a grand piano,
(d) a molecular model of cis‐Fe(bipy)2Cl2
23.80 (a)
(b) These complexes are colored because the crystal‐field splitting energy, , is in the
visible portion of the electromagnetic spectrum. Visible light with  = hc/is
absorbed, promoting one of the d‐electrons into a higher energy d‐orbital. The
remaining wavelengths of visible light are reflected or transmitted; the
combination of these wavelengths is the color we see.
(c) [Cr(NH3)6]3+ will absorb light with higher energy. NH3 is in the middle of the
spectrochemical series, and causes a larger  than Br−, a weak‐field ligand.
Because  and  are inversely related, larger  corresponds to higher energy and
shorter .
23.81 (a) Formally, the two Ru centers have different oxidation states; one is +2 and the
other is +3.
(b)
(c) There is extensive bonding-electron delocalization in the isolated pyrazine

molecule. When pyrazine acts as a bridging ligand, its delocalized molecular
orbitals provide a pathway for delocalization of the “odd” d-electron in the Creutz-
Taube ion. The two metal ions appear equivalent because the odd d-electron is
delocalized across the pyrazine bridge.
23.82 According to the spectrochemical series, the order of increasing  for the ligands is
Cl– < H2O < NH3. (The tetrahedral Cl– complex will have an even smaller  than an
703
octahedral one.) The smaller the value of , the longer the wavelength of visible light
absorbed. The color of light absorbed is the complement of the observed color. A blue
complex absorbs orange light (580 to 650 nm), a pink complex absorbs green light (490 to
560 nm), and a yellow complex absorbs violet light (400 to 430 nm). Because [CoCl4]2–
absorbs the longest wavelength, it appears blue. [Co(H2O)6]2+ absorbs green and appears
pink, and [Co(NH3)6]3+ absorbs violet and appears yellow.
23.83 (a) oxyhemoglobin deoxyhemoglobin
low spin, high spin,

no unpaired electrons 4 unpaired electrons
(b) In deoxyhemoglobin, H2O is bound to Fe in place of O2.

(c) The two forms of hemoglobin have different colors because they absorb different
wavelengths of visible light. They differ by just the H2O or O2 ligand, which means
that the two ligands have slightly different ligand fields. Oxyhemoglobin appears red
and absorbs green light, whereas deoxyhemoglobin appears bluish and absorbs
longer wavelength yellow-green light. O2 has a stronger ligand field than H2O.
(d) According to Table 18.1, air is 20.948 mole percent O2. This translates to 209,480 ppm
O2. This is approximately 500 times the 400 ppm concentration of CO in the
experiment. If air with a CO concentration 1/500th that of O2 converts 1/10 of the
oxyhemoglobin to carboxyhemoglobin, the equilibrium constant for binding CO is
much larger than that for binding O2.
(e) If CO is a stronger field ligand than O2, carboxyhemoglobin will absorb shorter
wavelengths than hemoglobin. It will absorb blue-green light and appear orange-
red.
23.84 (a) The term isoelectronic means that the three ions have the same number of
electrons.
(b) In each ion, the metal is in its maximum oxidation state and has a d 0 electron
configuration. That is, the metal ions have no d-electrons, so there should be no
d-d transitions.
(c) A ligand-metal charge transfer transition occurs when an electron in a filled ligand
orbital is excited to an empty d-orbital of the metal.
(d) Absorption of 565 nm yellow light by MnO 4– causes the compound to appear
violet, the complementary color. CrO 42– appears yellow, so it is absorbing violet
light of approximately 420 nm. The wavelength of the LMCT transition for
704
chromate, 420 nm, is shorter than the wavelength of LCMT transition in
permanganate, 565 nm. This means that there is a larger energy difference
between filled ligand and empty metal orbitals in chromate than in
permanganate.
(e) UV. A white compound indicates that no visible light is absorbed. Going left on
the periodic chart from Mn to Cr, the absorbed wavelength got shorter and the
energy difference between ligand and metal orbitals increased. The 420 nm
absorption by CrO 4– is at the short wavelength edge of the visible spectrum. It is
not surprising that the ion containing V, further left on the chart, absorbs at a still
shorter wavelength in the ultraviolet region and that VO 43– appears white.
23.85 The higher the oxidation state of the metal, the smaller the energy separation between
the ligand orbitals and the empty d-orbitals on the metal. The oxidation states of the
metals in the tetrahedral oxoanions are: Mn, +7; Cr, +6; V, +5. From Solution 23.84, the
energy separation between the ligand orbitals and the empty d-orbitals on the metals
increases in the order Mn < Cr < V.
23.86 Application of pressure would result in shorter metal

ion–ligand distances. This would have the effect of
increasing the ligand‐electron repulsions, and would
result in a larger splitting in the d‐orbital energies. Thus,
application of pressure should result in a shift in the
absorption to a higher energy and shorter wavelength.
23.87 (a)
(b) sodium dicarbonyltetracyanoferrate(II)

(c) +2, 6 d-electrons
(d) We expect the complex to be low spin. Cyanide (and carbonyl) are high on the
spectrochemical series, which means the complex will have a large  splitting
characteristic of low spin complexes.
23.88
705
23.89 A large part of the metal-ligand interaction is electrostatic attraction between the
positively charged metal and the fully or partially negatively charged ligand. For
the same ligand, the greater the charge on the metal or the shorter the M–L separation,
the stronger the interaction and the more stable the complex. The greater positive
charge and smaller ionic radius of a metal in the 3+ oxidation state means that, for the
same ligand, complexes with metals in the 3+ state are more stable than those with
metals in the 2+ state.
23.90 (a) Only one (b) Two
(c) Four; two are geometric, the other two are stereoisomers of each of these.
23.91 (a) Zero. The CO ligand is a neutral molecule and the charge on the complex is zero,
so chromium must be present as Cr(0).
(b) The electron configuration of a Cr atom in the absence of a ligand field is
[Ar]4s23d4. An octahedral complex with 4 d-electrons would have unpaired
electrons and be paramagnetic. In order for the complex to be diamagnetic,
all valence electrons must be paired. The electron configuration of Cr in the
complex is [Ar]3d6. In a strong field complex, the 6 d-electrons will be paired in the
three lower energy d orbitals.
(c) A colorless complex has no d-d electron transitions. This indicates a large  for
the complex, which means CO is a strong-field ligand.
(d) hexacarbonylchromium(0)
Integrative Exercises
23.92 (a)
(b) The pKa of pure water is 14, that of carbonic anhydrase is 7.5. The active site of
carbonic anhydrase is much more acidic than the bulk water. In carbonic
anhydrase, the Zn 2+ ion withdraws electron density from the O atom of water.
The electronegative oxygen atom compensates by withdrawing electron-density
706
from the O — H bond. The O — H bond is polarized and H becomes more
ionizable, more acidic than in the bulk solvent. This is similar to the effect of an
electronegative central atom in an oxyacid such as H 2SO 4.
(c) When the water molecule is deprotonated, the ligand coordinated to water
becomes hydroxide ion, OH–. The three N atoms are unaffected.
(d) In [Zn(H2O)6]2+, the Zn 2+ ion has six bound O atoms from which to withdraw
electron density. Each O atom donates less electron density than the single
O atom in carbonic anhydrase and each O atom withdraws less electron density
from its O — H bonds. The O — H bonds in [Zn(H2O)6]2+ are less polarized and
less acidic than those in carbonic anhydrase. [Zn(H2O)6]2+ is a weaker acid and
has a higher pKa than carbonic anhydrase.
(e) No, we do not expect carbonic anhydrase to have a deep color like hemoglobin.
The Zn 2+ ion is a d10 metal center. Its d-orbitals are completely occupied and
there is no possibility for the d-d transitions that lead to colored complexes.
23.93 (a) Both compounds have the same general formulation, so Co is in the same (+3)
oxidation state in both complexes.
(b) Cobalt(III) complexes are generally inert; that is, they do not rapidly exchange
ligands inside the coordination sphere. Therefore, the ions that form precipitates
in these two cases are probably outside the coordination sphere. The dark violet
compound A forms a precipitate with BaCl 2(aq) but not AgNO 3(aq), so it has
SO 42– outside the coordination sphere and coordinated Br –, [Co(NH 3) 5Br]SO 4.
The red-violet compound B forms a precipitate with AgNO 3(aq) but not
BaCl 2(aq) so it has Br – outside the coordination sphere and coordinated SO 42–,
[Co(NH 3) 5SO 4]Br.
(c) Compounds A and B have the same formula but different properties (color,
chemical reactivity), so they are isomers. They vary by which ion is inside the
coordination sphere, so they are coordination sphere isomers.
(d) Compound A is an ionic sulfate and compound B is an ionic bromide, so both are
strong electrolytes. According to the solubility guidelines in Table 4.1, both
should be water-soluble.
23.94 Determine the empirical formula of the complex, assuming a 100 g sample.
1 mol Fe
9.38 g Fe   0.168 mol Fe; 0.168/0.168  1
55.85 g Fe
707
1 mol C
60.53 g C   5.044 mol C; 5.044 / 0.168  30
12.0 g C
1 mol H
4.06 g H   4.06 mol H; 4.06/0.168  24
1.0 g H
1 mol N
14.12 g N   1.01 mol N; 1.01/0.168  6
14.0 g C
1 mol Cl
11.91 g Cl   0.336 mol Cl; 0.366/0.168  2
35.45 g Cl
There are 10 C, 8 H and 2 N atoms per bipyridine ligand. Therefore, a total of three
bipyridine ligands are coordinated to the Fe center. To match the conductivity of
K2[CuCl4], the 6 coordination sites of Fe are all coordinated by the bipyridine ligand in
the coordination sphere. Thus, the compound is [Fe(bipy)3]Cl2.
23.95 (a) G = –nFE. The positive E values for both sets of complexes correspond to
–G values. Negative values of G mean that both processes are spontaneous.
For both o-phen and CN– ligands, the Fe(II) complex is more thermodynamically
favorable than the Fe(III) complex.
(b) The CN– complex, with the smaller positive E value, is more difficult to reduce.
(c) That both the Fe(II) complexes are low spin means that both CN– and o-phen are
strong-field ligands. The negatively charged CN– has a stronger electrostatic
interaction with Fe3+ than the neutral o-phen has. This stabilizes the Fe(III)
complex of CN– relative to the Fe(III) complex of o-phen, which reduces the
driving force for reduction of [Fe(CN)6]3– relative to reduction of [Fe(o-phen)3]3+.
The E value and magnitude of G for the reduction of the CN– complex are
thus smaller than those values for the o-phen complex.
23.96 Determine the empirical formula of the complex, assuming a 100 g sample.
1 mol Pt
65.02 g Pt   0.333 mol Pt; 0.333/0.333  1
195.1 g Pt
1 mol H
2.02 g H   2.02 mol H; 2.02/0.333  6
1.0 g H
1 mol N
9.34 g N   0.667 mol N; 0.667/0.333  2
14.0 g N
1 mol Cl
23.63 g Cl   0.667 mol Cl; 0.336/0.168  2
35.45 g Cl
The chemical formula is [Pt(NH3)2Cl2]. This should be a neutral square‐planar complex

of Pt(II), a nonelectrolyte. Because it has a net dipole moment, we can infer that it must
be the cis isomer.
708
23.97 (a) The reaction that occurs increases the conductivity of the solution by producing a
greater number of charged particles, particles with higher charges, or both. It is
likely that H2O from the bulk solvent exchanges with a coordinated Br– according to
the reaction below. This reaction would convert the 1:1 electrolyte, [Co(NH3)4Br2]Br,
to a 1:2 electrolyte, [Co(NH3)3(H2O)Br]Br2.
(b) [Co(NH 3) 4Br 2] +(aq) + H 2O(l)  [Co(NH 3) 4(H 2O)Br] 2+(aq) + Br –(aq)
(c) Before the exchange reaction, there is one mole of free Br– per mole of complex. mol
Br– = mol Ag+
M = mol/L; L AgNO 3 = mol AgNO 3/M AgNO 3
3.87g com plex 1m olcom plex

  0.02500 L soln used 
0.500 L soln 366.77 g com plex
5.276  104  5.28  104 m olcom plex
1m olBr 1m olA g 1L A g (aq)

5.276  104 m olcom plex   

1m olcom plex 1m olBr 0.0100 m olA g (aq)
 0.05276 L  52.8 m L A gN O 3(aq)
(d) After the exchange reaction, there are 2 mol free Br – per mol of complex. Because
M AgNO 3(aq) and volume of complex solution are the same for the second
experiment, the titration after conductivity changes will require twice the volume
calculated in part (c), 105.52 = 106 mL of 0.0100 M AgNO 3(aq).
23.98 Calculate the concentration of Mg 2+ alone, and then the concentration of Ca 2+ by

difference. M  L = mol
0.0104 m olED TA 1m olM g2 24.31g M g2 1000 m g

 0.0187 L   
1L 1m olED TA 1m olM g2 g
1
  47.28  47.3 m g M g2 /L
0.100 L H 2O
0.0104 M ED TA  0.0315 L  m ol(C a2  M g2 )

0.0104 M ED TA  0.0187 L  m olM g2
0.0104 M ED TA  0.0128 L  m olC a2
1m olC a2 40.08 g C a2 1000 m g 1

0.0104 M ED TA  0.0128 L   2
 
1m olED TA 1m olC a g 0.
100 L H 2O
 53.35  53.4 m g C a2 /L
23.99 Use Hess’ law to calculate G o for the desired equilibrium. Then  G o = –RT ln K to
calculate K.
709
H b  C O  H bC O  G o   80 kJ
H bO 2  H b  O 2  G o  70 kJ
H bO 2  H b  C O  H bC O  H b  O 2
H bO 2  C O  H bC O  O 2  G o   10 kJ
G o ( 10 kJ) 1000 J

G   R T ln K ,ln K     4.036  4.04
RT 8.314 J/K -m ol 298 K kJ
K = e 4.04 = 56.61 = 57
198,580 J 1 mol
23.100   3.30  1019  3.30  1019 J/photon
1 mol 6.022  1023 molecules
E = h = 3.30  10 –19 J;  = E/h

 = 3.30  10 –19 J/6.626  10 –34 J - s = 4.98  10 14 = 4.98  10 14 s –1
2.998  108 m/s

 14  1
 6.02  107 m  602 nm
4.98  10 s
We expect that this complex will absorb in the visible, at around 600 nm. It will thus
exhibit a blue color (Figure 23.25).
23.101 The process can be written:

2 H + (aq)  2 e  H 2 (g) o
E red  0.0 V
Zn(s)  Zn 2  (aq)  2 e  o
E red   0.7628 V
Zn 2  (aq)  4 NH3 (aq)  [Zn(NH3 ) 4 ]2  E of  ?
2 H + (aq)  Zn(s)  4 NH3 (aq)  [Zn(NH3 ) 4 ]2  + H 2 (g) E  1. 04 V
[Zn(NH3 ) 24  ]
Kf 
[Zn 2  ][NH3 ]4
Because we know Eo values for two steps and the overall reaction, we can calculate “Eo”
for the formation reaction and the Kf, using Eo.
0.0592 V
E of  log K f
n
n  E of
log K f 
0.0592 V
E cell  1.04 V  0.00 V  ( 0.7628 V)  E of ; E of  0.2772 V
2  0.2772 V
log K f   9.365; K f = 2.32  10 9 L4/mol4
0.0592 V
Check: Calculate the concentration of free Zn2+ ions and the corresponding reduction
potential of the Zn2+/Zn half cell; the difference, 0.00 V (standard hydrogen electrode) –
Ered(Zn2+/Zn), should be equal to the emf of the cell.
710
[Zn(NH3 ) 24  ] 1
[Zn 2  ]    4.32  1010 mol/L
K f  [NH 3 ]4 2.32  109  14
0.0592 V 1
E red (Zn 2  )  E °red  log   0.7628 V + 0.0296 V lo g ( 4.32  1010 ) =  1.04 V
2 [Zn 2  ]
711

M23 Wils2248 14 Se C23

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Transition Metals

(a) Coordination number is 4

The ligand is polydentate. If bound to a single metal center, it is likely to be

(a) Diaminodichloroplatinum(II). If the geometry is square planar, the prefix cis-

(c) The tetrahedral molecule would be paramagnetic. Platinum(II) is a d8 transition

Solve. (1) has all 90 angles between similar ligands.

23.6 Analyze. Given four structures, decide which are chiral.

The Transition Metals (Section 23.1)

23.16 (a) Ru3+, [Kr]4d5; 5 valence d‐electrons

(d) W6+, [Xe]4f14; 0 valence d‐electrons

23.18 Antiferromagnetic materials cannot be used to make permanent magnets. In an

(b) In an antiferromagnetic material, spins on coupled atoms are oppositely aligned,

Transition-Metal Complexes (Section 23.2)

23.24 (a) [Cr(H 2O) 6]3+

Common Ligands in Coordination Chemistry (Section 23.3)

monodentate ligand, only N atom has a nonbonded pair of electrons

monodentate ligand, only P atom has a nonbonded pair of electrons

either monodentate or bidentate

unlikely to act as a ligand, no nonbonded pairs of electrons

23.28 (a) 2 coordination sites, 2 O donor atoms

(b) 2 coordination sites, 2 N donor atoms

23.30 (a) 6 (b) 6 (c) 4 (d) 6

Nomenclature and Isomerism in Coordination Chemistry (Section 23.4)

(d) (NH4)2[Co(C2O4)2(H2O)2] (e) [Co(bipy)3]2(SO4)3

(c) (NH3)2[PdCl6] (d) [Ni(NH3)2(C2O4)]

(b) mercury(II) tetrathiocyanatocobaltate(II)

(d) pentaamminecarbonatocobalt(III) sulphate

23.38 (a) sodium pentacyanonitrosylferrate(II)

(b) pentaammineoxocobalt(III) bromide

(c) sodium tetrabromonickelate(II)

(d) hexaaquarhodium(III) dicyanoargentate(I)

23.44 (a) Two geometric isomers (enantiomers)

(c) No geometric isomers

23.46 (a) Not chiral. A square planar complex cannot be chiral.

Color and Magnetism in Coordination Chemistry; Crystal-Field Theory

23.48 (a) E(J/photon) = hc/.  = hc/E.

6.626  1034 J-s 2.998  108 m /s

23.58 (a) Cr3+, d3 (b) Zr2+, d2 (c) Cu2+, d9

23.61 Analyze/Plan. Follow the logic in Sample Exercise 23.7. Solve.

1 unpaired electron 0 unpaired electrons 1 unpaired electron

5 unpaired electrons 3 unpaired electrons 4 unpaired electrons

(a) cis‐bromochlorodinitroplatinate(II) ion

23.73 (a) Valence electrons: 2P + 6C + 16H = 10 + 24 + 16 = 50 e –, 25 e – pr

(b) Magnesium. Chlorophylls are magnesium-containing porphyrins in plants. They

23.79 (b) a computer keyboard,

(c) There is extensive bonding-electron delocalization in the isolated pyrazine

23.83 (a) oxyhemoglobin deoxyhemoglobin

low spin, high spin,

(b) In deoxyhemoglobin, H2O is bound to Fe in place of O2.

23.86 Application of pressure would result in shorter metal

(b) sodium dicarbonyltetracyanoferrate(II)

23.90 (a) Only one (b) Two

The chemical formula is [Pt(NH3)2Cl2]. This should be a neutral square‐planar complex

M = mol/L; L AgNO 3 = mol AgNO 3/M AgNO 3

3.87g com plex 1m olcom plex

1m olBr 1m olA g 1L A g (aq)

23.98 Calculate the concentration of Mg 2+ alone, and then the concentration of Ca 2+ by

0.0104 m olED TA 1m olM g2 24.31g M g2 1000 m g

0.0104 M ED TA  0.0315 L  m ol(C a2  M g2 )

1m olC a2 40.08 g C a2 1000 m g 1

G o ( 10 kJ) 1000 J

E = h = 3.30  10 –19 J;  = E/h

2.998  108 m/s