Inorganic Chemistry 5th Edition

Miessler Solutions Manual

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 Chapter 9 Coordination Chemistry I: Structures and Isomers 123

CHAPTER 9: COORDINATION CHEMISTRY I: STRUCTURES AND

ISOMERS
9.1 Hexagonal: C2v C2v D2h
Hexagonal pyramidal: Cs Cs C2v
Trigonal prismatic: Cs C2v C2
Trigonal antiprismatic: Cs C2 C2h
The structures with C2 symmetry would be optically active.

9.2 a. dicyanotetrakis(methylisocyano)iron(II) or dicyanotetrakis(methylisocyano)iron(0)

b. rubidium tetrafluoroargentate(III) or rubidium tetrafluoroargentate(1–)

c. cis- and trans-carbonylchlorobis(triphenylphosphine)iridium(I) or cis- and trans-

carbon ylchlorobis(triphenylphospine)iridium(0)

d. pentaammineazidocobalt(III) sulfate or pentaammineazidocobalt(2+) sulfate

e. diamminesilver(I) tetrafluoroborate(III) or diamminesilver(1+) tetrafluoroborate(1–)

–
(The BF4 ion is commonly called “tetrafluoroborate.”)

9.3 a. tris(oxalato)vanadate(III) or tris(oxalato)vanadate(3–)

b. sodium tetrachloroaluminate(III) or sodium tetrachloroaluminate(1–)

c. carbonatobis(ethylenediamine)cobalt(III) chloride or
carbonatobis(ethy lenediamine)cobalt(1+) chloride

d. tris(2,2-bipyridine)nickel(II) nitrate or tris(2,2-bipyridine)nickel(2+) nitrate (The

IUPAC name of the bidentate ligand, 2,2-bipyridyl may also be used; this ligand is most
familiarly called “bipy.”)

e. hexacarbonylmolybdenum(0) (also commonly called “molybdenum hexacarbonyl”).

The (0) is often omitted.

9.4 a. tetraamminecopper(II) or tetraamminecopper(2+)

b. tetrachloroplatinate(II) or tetrachloroplatinate(2–)

c. tris(dimethyldithiocarbamato)iron(III) or tris(dimethyldithiocarbamato)iron(0)

d. hexacyanomanganate(II) or hexacyanomanganate(4–)

e. nonahydridorhenate(VII) or nonahydridorhenate(2–) (This ion is commonly called

“enneahydridorhenate.”)

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124 Chapter 9 Coordination Chemistry I: Structures and Isomers

9.5 a. triamminetrichloroplatinum(IV) or triamminetrichloroplatinum(1+)

b. diamminediaquadichlorocobalt(III) or diamminediaquadichlorocobalt(1+)

c. diamminediaquabromochlorocobalt(III) or diamminediaquabromochlorocobalt(1+)

d. triaquabromochloroiodochromium(III) or triaquabromochloroiodochromium(0)

e. dichlorobis(ethylenediamine)platinum(IV) or dichlorobis(ethylenediamine)platinum(2+)
or dichlorobis(1,2-ethanediamine)platinum(IV) or dichlorobis(1,2-
ethanediamine)platinum(2+)

f. diamminedichloro(o-phenanthroline)chromium(III) or diamminedichloro(o-
phenanthroline)chro mium(1+) or diamminedichloro(1,10-phenanthroline)chromium(III)
or diamminedichloro(1,10-phenanthroline)chromium(1+)

g. bis(2,2-bipyridine)bromochloroplatinum(IV) or bis(2,2-
bypyridine)bromochloroplatinum(2+)
or bis(2,2-bipyridyl)bromochloroplatinum(IV) or bis(2,2-
bipyridyl)bromochloroplatinum(2+)

h. dibromo[o-phenylene(dimethylarsine)(dimethylphosphine)]rhenium(II) or
dibrom o[o-phenylene(dimethylarsine)(dimethylphosphine)]rhenium(0) or
dibrom o[1,2-phenylene(dimethylarsine)(dimethylphosphine)]rhenium(II) or
dibrom o[1,2-phenylene(dimethylarsine)(dimethylphosphine)]rhenium(0)

i. dibromochlorodiethylenetriaminerhenium(III) or
dibrom ochlorodiethylenetriaminerhenium(0) or dibromochloro(2,2-
diam inodiethylamine)rhenium(III) or dibromochloro(2,2-
diam inodiethylamine)rhenium(0)

9.6 a. dicarbonylbis(dimethyldithiocarbamato)ruthenium(III) or
dicarbonylbis(dimethyldithiocarbamato)ruthenium(1+)

b. trisoxalatocobaltate(III) or trisoxalatocobaltate(3–)

c. tris(ethylenediamine)ruthenium(II) or tris(ethylenediamine)ruthenium(2+)

d. bis(2,2-bipyridine)dichloronickel(II) or bis(2,2-bipyridine)dichloronickel(2+)

9.7 a. Bis(en)Co(III)-µ-amido-µ-hydroxobis(en)Co(III)

4+
N N

H2
N N N
Co Co
N O N
H

N N

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 Chapter 9 Coordination Chemistry I: Structures and Isomers 125

b. Diaquadiiododinitritopalladium(IV)

I H2O

ONO OH2 ONO I

Pd Pd
H2O ONO H 2O ONO

I I

I I

ONO OH2 ONO OH2

Pd Pd
ONO OH2 H 2O I

I ONO

I I

H 2O I I OH2
Pd Pd
ONO ONO ONO ONO

H2O OH2

enantiomers

c. Fe(dtc)3
S S
–
S CH3
S
S S S S
Fe Fe = C N
S S S S S
S H
S S

At low temperature, restricted rotation about the C—N bond can lead to additional
isomers as a consequence of the different substituents on the nitrogen. These isomers can
be observed by NMR.

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126 Chapter 9 Coordination Chemistry I: Structures and Isomers

9.8 a. triammineaquadichlorocobalt(III) chloride Isomers are of the cation:

+ + +
H2O Cl NH3

H3N Cl H3N OH2 H2O NH3

Co Co Co
H 3N NH3 H3N NH3 Cl NH3

Cl Cl Cl
cis trans

mer fac

b. -oxo-bis(pentammine-chromium(III)) ion
4+
H3N H3N H3N NH3

O
Cr Cr
H3N NH3

H3N NH3 NH3 NH3

c. potassium diaquabis(oxalato)manganate(III) Isomers are of the anion:

– – –
O O H2O

O O O O O O
Mn Mn Mn
H2O O O OH2 O O

H2O OH2 H2O

cis enantiomers trans

Cl NH3

9.9 a. cis-diamminebromochloroplatinum(II) Pt

Br NH3

b. diaquadiiododinitritopalladium(IV) H2O ONO

Pt
ONO OH2

O
O O C O
C C C CO
c. tri--carbonylbis(tricarbonyliron(0))
Fe Fe

OC CC CO
O O
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 Chapter 9 Coordination Chemistry I: Structures and Isomers 127

9.10 O
CH2 C
H2 N O – = N O

O O N N

N N N N O N N O
M M M M
O O O O N O O N

N N O O
fac mer
9.11 M(AB)3
B B A A

A A A A B A A B
M M M M
B B B B A B B A

A A B B
fac mer

9.12 a. [Pt(NH3)3Cl3]+
+ Cl
+
NH 3

Cl NH3 H3N NH3

Pt Pt
Cl NH3 Cl NH3

Cl Cl
fac mer

b. [Co(NH3)2(H2O)2Cl2]+

+ + + +
NH3 Cl NH3 NH3

H 2O NH3 H 2O NH3 Cl OH2 Cl OH2

Co Co Co Co
Cl OH2 H 2O NH3 Cl OH2 H2 O Cl

Cl Cl NH3 NH3

+ +
OH2 H 2O

H 2O NH3 H 3N OH2
Co Co
Cl NH3 H3N Cl

Cl Cl
enantiomers

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128 Chapter 9 Coordination Chemistry I: Structures and Isomers

c. [Co(NH3)2(H2O)2BrCl]+
+ + + +
OH2 Cl NH3 NH3

H 3N Br H 2O NH3 Br OH2 Cl OH2

Co Co Co Co
H 3N Cl H 2O NH3 Cl OH2 H2 O Br

OH2 Br NH3 NH3

+ + + +
OH2 H2O OH2 H2O

H 2O NH3 H 3N OH2 H2 O NH3 H3 N OH2

Co Co Co Co
Br NH3 H 3N Br Cl NH3 H3N Cl

Cl Cl Br Br
enantiomers enantiomers

d. Cr(H2O)3BrClI

OH2 H2O

H2 O OH2 H2 O OH2
Cr Cr
Cl I I Cl

Br Br
enantiomers

OH2 OH2 OH2

Cl OH2 I OH2 Cl OH2

Cr Cr Cr
H2 O Br H 2O Br H2 O I

I Cl Br

e. [Pt(en)2Cl2]2+

2+ 2+ 2+
N N Cl

N N N N N N
Pt Pt Pt
Cl N N Cl N N

Cl Cl Cl

cis enantiomers trans

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 Chapter 9 Coordination Chemistry I: Structures and Isomers 129

f. [Cr(o-phen)(NH3)2Cl2]+
+ +
+ +

N N
N N
N Cl N NH3
N NH3 H 3N N
Cr Cr
Cr Cr Cl NH3 H3N Cl
Cl NH3 H3N Cl
NH3 Cl
Cl Cl
enantiomers trans Cl ligands trans NH3 ligands

g. [Pt(bipy)2BrCl]2+ 2+ 2+

2+
Br N N

N N N Br Br N
Pt Pt Pt
N N Cl Cl
N N
Cl N N
enantiomers

h. Re(arphos)2Br2 Abbreviating the bidentate ligands As P :

Br Br P P

P P P As Br As As Br
Re Re Re Re
As As As P Br As As Br
Br Br P P
 

As As As As

Br P P Br Br P P Br
Re Re Re Re
Br P P Br Br As As Br

As As P P
   

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130 Chapter 9 Coordination Chemistry I: Structures and Isomers

i. Re(dien)Br2Cl
Cl Cl Br

N Br Br N N Cl
Re Re Re
N Br Br N N Br

N N N

Br Cl

N Cl N Br
Re Re
N N N N

Br Br

9.13 a. M(ABA)(CDC)

C A B B

A D C B C A A C
M M M M
B A D A D A A D
C C C C

b. M(ABA)(CDE)

C A A

A D C B B C
M M M
B A D A A D
E E E

B B

C A A C
M M
D A A D

E E

A A

C A A C
M M
D B B D
E E

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 Chapter 9 Coordination Chemistry I: Structures and Isomers 131

9.14
A A A

C B A B B A
M M M
B C B C C B
A C C

A A C C

A B B A A A A A
M M M M
B C C B B B B B
C C C C

B B B B

A C C A A A A A
M M M M
B A B B B C C B
C C C C

9.15 a. The “softer” phosphorus atom bonds preferentially to the soft metal Pd (see Section 6.6.1).
b, c. Abbreviating the bidentate ligands N P :

Cl Cl P P

P P P N Cl N N Cl
Ni Ni Ni Ni
N N N P Cl N N Cl
Cl Cl P P
 

N N N N

Cl P P Cl Cl P P Cl
Ni Ni Ni Ni
Cl P P Cl Cl N N Cl
N N P P
   

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132 Chapter 9 Coordination Chemistry I: Structures and Isomers

9.16 a, b. Abbreviating the bidentate ligands N P and O S :

Cl Cl

S P S N
M M
O N O P
Cl Cl

N N P P

Cl P P Cl Cl N N Cl
M M M M
Cl O O Cl Cl O O Cl

S S S S
   

N N P P

Cl P P Cl Cl N N Cl
M M M M
Cl S S Cl Cl S S Cl

O O O O
   

N –

9.17 The single C–N stretching frequency indicates a trans

structure for the cyanides (the symmetric stretch of the C
C—N bonds is not IR active), while the two C–O bonds O
C
O
C
indicate a cis structure for the carbonyls (both the Co
symmetric and antisymmetric C–O stretches are IR Br Br
active). As a result, the bromo ligands are also cis. C

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 Chapter 9 Coordination Chemistry I: Structures and Isomers 133

9.18 There are 18 isomers overall, six with the chelating ligand in a mer geometry and 12 with
the chelating ligand in a fac geometry. All are enantiomers. They are all shown below, with
dashed lines separating the enantiomers.

N N N N N N

P Br Br P P Br Br P P NH 3 H3N P
M M M M M M
As OH2 H2O As As NH3 H 3N As As OH2 H2 O As

NH3 NH3 OH2 OH2 Br Br

N N N N N N

P OH2 H2O P P NH3 H3 N P P OH2 H 2O P

M M M M M M
As Br Br As As Br Br As As NH3 H3N As

NH3 NH3 OH2 OH2 Br Br

NH3 NH3 OH2 OH2 NH3 NH3

P N N P P N N P P N N P
M M M M M M
As OH2 H2O As As NH3 H3N As As Br Br As

Br Br Br Br OH2 OH2

9.19 a.  b.  c.  d. 

9.20 All are chiral if the ring in b does not switch conformations.

9.21 20b  20c top ring: , bottom ring: 

O Mo S Mo
9.22 a, b. 1. Mo O Mo O

Mo S Mo O
O W O W
Cs C3v

O Mo S Mo
2. Mo O Mo S

Mo S Mo O
S W O W
Cs Cs

S Mo Mo S O Mo Mo O
Mo O O Mo Mo S S Mo
3.
Cr O O Cr Cr O O Cr
Se W W Se Se W W Se
C1 C1 C1 C1

Se Mo Mo Se O Mo Mo O
Mo O O Mo Mo Se Se Mo

Cr O O Cr Cr O O Cr
S W W S S W W S
C1 C1 C1 C1

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134 Chapter 9 Coordination Chemistry I: Structures and Isomers

S Mo S Mo
Mo Se Mo Se

Cr O W O
O W O Cr
Cs Cs

c. Yes, provided the structure has no symmetry or only Cn axes. Examples are the
structures with C1 symmetry in part a.

9.23 The 19F doublet is from the two axial fluorines (split by the equatorial fluorine). F
+

The 19F triplet is from the equatorial fluorine (split by the two axial fluorines). O
Os F
The two doubly bonded oxygens are equatorial, as expected from VSEPR O
considerations. Point group: C2v F
9.24 Examples include both cations and anions:
– – – – –
[Cu(CN)2] , [Cu2(CN)3] , [Cu3(CN)4] , [Cu4(CN)5] , [Cu5(CN)6]
[Cu2(CN)]+, [Cu3(CN)2]+, [Cu4(CN)3]+, [Cu5(CN)4]+, [Cu6(CN)5]+
Based primarily on calculations (rather than experimental data), Dance et al. proposed
linear structures such as the following:
–
[Cu(CN)2] : NC—Cu—CN
–
[Cu2(CN)3] : NC—Cu—CN—Cu—CN
–
[Cu3(CN)4] : NC—Cu—CN—Cu—CN—Cu—CN
+
[Cu2(CN)] : Cu—CN—Cu
+
[Cu3(CN)2] : Cu—CN—Cu—CN—Cu
+
[Cu4(CN)3] : Cu—CN—Cu—NC—Cu—CN—Cu
Where 2-coordinate copper appears in these ions, the geometry around the Cu is linear, as
expected from VSEPR.

9.25 The bulky mesityl groups cause sufficient crowding that the phosphine ligands can show
chirality (C3 symmetry) and can be considered as similar to left-handed (PL) and HC 3

right-handed (PR) propellers. If two P(mesityl)3 phosphines are attached in a CH3

linear arrangement to a gold atom, three isomers are possible:
H 3C
PL—Au—PL PR—Au—PR PL—Au—PR mesityl
(PR—Au—PL is equivalent to PL—Au—PR, as can best be seen with models.) NMR data
at low temperature support the presence of these isomers, which interconvert at higher
temperatures.

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 Chapter 9 Coordination Chemistry I: Structures and Isomers 135

9.26 The point group is D3h. A representation  based on the nine 1s orbitals
of the hydride ligands is:
 

D3h E 2C3 3C2 h 2S3 3v 
 Re
 9 0 1 3 0 3

A1 1 1 1 1 1 0 z2 
E 2 –1 0 2 –1 0 (x, y), (x2–y2, xy) 
A2 1 1 –1 –1 –1 1 z 
E 2 –1 0 –2 1 0 (xz, yz) = H

The representation  reduces to 2 A1 + 2 E + A2 + ECollectively these representations

match all the functions for s (totally symmetric, matching A1), p, and d orbitals of Re, so all the s,
p, and d orbitals of the metal have suitable symmetry for interaction. (The strength of these
interactions will also depend on the match in energies between the rhenium orbitals and the 1s
orbital of hydrogen.)
9.27

NN NN
NN
O Cr O O Cr O
O Cr O
OO OO OO O
O OO OO
O Mn O O Mn
Mn O O Mn O O O
O O O O
O O OO O
O OO O OO O
O Cr O O Cr O
O Cr O
NN NN
NN

9.28 N

N N
O O

N Co N
N N
N O O N
N N
O O
O O
Co Co
O
O
O N O
N N
N N

N N N N

N N
N N
O N O
O O
Co Co
O O
O O
N N
N O O N
N N
N Co N

O O
N N

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136 Chapter 9 Coordination Chemistry I: Structures and Isomers

9.29 a. Cu(acacCN)2: D2h tpt: C2v

b. C6

9.30 All four metal-organic frameworks studied (MOF-177, Co(BDP), Cu-BTTri, Mg 2 (dobdc) ) are
significantly more effective at adsorbing carbon dioxide relative to adsorbing hydrogen. This is
attributed, in part, to the higher polarizability of CO 2 relative to that of H 2 . The formation of an
induced dipole in these gases by exposed cations within MOFs is an important prerequisite for
adsorption. The two MOF properties that most strongly correlate with CO 2 adsorption capacity
are MOF surface area and MOF accessible pore volume. As these values (tabulated below)
increase, the CO 2 adsorption capacity increases.

MOF Surface Area ( m2 g ) Accessible Pore Volume ( cm3 g )

MOF-177 4690 1.59
Co(BDP) 2030 0.93
Cu-BTTri 1750 0.713
Mg 2 (dobdc) 1800 0.573

The graphs in Figure 1 of the reference clearly indicate that Mg 2 (dobdc) adsorbs the most CO 2
at 5 bar. The arrangement and concentration of open Mg 2+ cation sites on the Mg 2 (dobdc)
surface is hypothesized to render this MOF more susceptible to CO 2 adsorption. This MOF,
along with Cu-BTTri, which also features exposed metal sites, are identified as the best prospects
for CO 2 H 2 separation.

9.31 The synthesis and application of amine-functionalized MOFs for CO 2 adsorption is the general
topic of the reference. While the M 2 (dobdc) series of MOFs were proposed as excellent
candidates for this functionalization (on the basis of their relatively large concentration of
exposed metal cation sites), their amine-functionalization proved difficult. This was attributed to
the relatively narrow MOF channels that may hinder amine diffusion into M 2 (dobdc) .
One hypothesized solution was to prepare a MOF with the M 2 (dobdc) structure-type, but with
larger pores. The wider linker dobpdc (below, along with dobdc for comparison) was used in the
hope of obtaining MOFs with larger pores.

O O

O O
O

O O
O

dobdc
O O

dobpdc

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 Chapter 9 Coordination Chemistry I: Structures and Isomers 137

Amine-functionalized Mg 2 (dobpdc) was prepared by mixing H 4 (dobpdc) , magnesium bromide,

and a small solvent volume (a mixture of N,N’-diethylformamide and ethanol) in a Pyrex
container. The mixture was heated in a microwave reactor, and the M 2 (dobpdc) collected by
filtration after cooling. Dried samples of Mg 2 (dobpdc) were then heated for roughly one hour at
420 °C under dynamic vacuum. After this “activation” step, Mg 2 (dobpdc) was stirred with an
excess of N,N’-dimethylethylenediamine (mmen) in hexanes for one day. Subsequent heating
under vacuum resulted in removal of residual solvents to afford mmen-functionalized
Mg 2 (dobpdc) . The “activation” step was found necessary to completely remove residual N,N’-
diethylformamide from the Mg 2+ coordination sites.

9.32 This reference discusses application of porphyrin-containing MOFs where the porphyrin provides
a binding site for Fe(III) and Cu(II). The precursor to the porphyrin linker (TCPP) is provided
below; the resulting carboxylates of this linker permit its incorporation into the MOF.
HOOC COOH

N
H

N N

H
N

HOOC COOH

The metallation options include premetallation and postmetallation. In premetallation,

H 4 -TCPP-Cu and H 4 -TCPP-FeCl , respectively, are used as reactants for the MOF synthesis. In
this case, the porphyrin linker and its bound metal ion are installed simultaneously into the MOF.
This general approach afforded MOF-525-Cu, MOF-545-Fe, and MOF-545-Cu. MOF-525-Fe
could not be obtained via this strategy. For this MOF, postmetallation was employed, via the
reaction of MOF-525 with Fe(III) chloride; Fe(III) ions were introduced into the MOF-525
porphyrin linkers via this method.

In terms of similarities and differences, MOF-545 can be metallated with both Fe(III) and Cu(II)
via a premetallation strategy, while MOF-525 requires alternate procedures for incorporation of
Cu(II) (premetallation) and Fe(III) (postmetallation), respectively.

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