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 transcarbon
ylchlorobis(triphenylphospine)iridium(0)

9.3

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.)

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

9.4

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.

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
9.5

Chapter 9 Coordination Chemistry I: Structures and Isomers

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.
or

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

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

bis(2,2-bipyridine)bromochloroplatinum(IV) or bis(2,2bypyridine)bromochloroplatinum(2+)
bis(2,2-bipyridyl)bromochloroplatinum(IV) or bis(2,2bipyridyl)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(2,2diam
inodiethylamine)rhenium(III) or dibromochloro(2,2diam
inodiethylamine)rhenium(0)
9.6

9.7

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+)

a.

Bis(en)Co(III)--amido--hydroxobis(en)Co(III)

N
N

Co
N

4+

N
H2
N
O
H

Co

N
N

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Chapter 9 Coordination Chemistry I: Structures and Isomers

b.

125

Diaquadiiododinitritopalladium(IV)
I
ONO

H2O

Pd

H2O

ONO

ONO

ONO

H 2O

I
OH2

ONO

OH2

H 2O

OH2
I

ONO
I

I
I

Pd

ONO

ONO

Pd

H 2O

Pd

Pd

ONO

OH2

ONO

ONO

OH2

Pd

ONO

OH2

H2O

enantiomers

c.

Fe(dtc)3

S
S
S

Fe

Fe

S
S

S
=

S
S

CH3

At low temperature, restricted rotation about the CN 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
9.8

Chapter 9 Coordination Chemistry I: Structures and Isomers

a.

triammineaquadichlorocobalt(III) chloride
+

H2O
H3N
H 3N

Co

Isomers are of the cation:

+

Cl

Cl

H3N

NH3

H3N

Co

OH2

H2O

NH3

Cl

Co
Cl

Cl

Cl

cis

trans
mer

b.

H3N

Cr

NH3

H3N

4+

NH3

H3N H3N

H3N

c.

fac

-oxo-bis(pentammine-chromium(III)) ion

Cr
NH3

NH3
NH3

potassium diaquabis(oxalato)manganate(III)

O
O
H2O

Mn

H2O

Mn

Isomers are of the anion:

H2O

OH2

OH2

H2O

trans

Cl

a.

Mn

cis enantiomers

9.9

NH3

cis-diamminebromochloroplatinum(II)

Pt
Br

NH3
I

b.

diaquadiiododinitritopalladium(IV)

H2O

Pt

ONO

ONO
OH2

c.

tri--carbonylbis(tricarbonyliron(0))

O
C

O O
C C
Fe
OC

NH3

O
C CO
Fe

CC
O O

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CO

NH3
NH3

Chapter 9 Coordination Chemistry I: Structures and Isomers

O

9.10
C

CH2

H2 N
O
N

= N

mer

M(AB)3
B
A

mer

[Pt(NH3)3Cl3]+

a.

fac

9.12

fac

9.11

127

NH 3
Cl

Pt

Cl

Cl

NH3

H3N

NH3

Cl

NH3

Pt

NH3

Cl

Cl

fac

mer

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

b.

NH3
H 2O
Cl

Co

Cl

NH3

H 2O

OH2

H 2O

Cl

Co

NH3

Cl

NH3

Cl

OH2

Cl

Co

Co

Cl

OH2

H2 O

NH3

H 3N

NH3

H3N

Cl

Co

Co
NH3

H 2O
OH2
Cl

Cl

enantiomers

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NH3

OH2

NH3

Cl

H 2O

NH3

OH2
Cl

128

Chapter 9 Coordination Chemistry I: Structures and Isomers

[Co(NH3)2(H2O)2BrCl]+

c.

OH2
H 3N
H 3N

Co

Br

H 2O

Cl

H 2O

Co

OH2

Br

Co

NH3

Br

NH3

Cl

Co

H 3N

NH3

H 3N

Cl

OH2

Cl

OH2

H2 O

H2 O

Co

Cl

Br

+
NH3

H3 N

NH3

H3N

+
OH2

Co

Cl

Br

enantiomers

d.

Br

H2O

Br

Cl

OH2

Co
NH3

OH2

OH2

Co

NH3

NH3

H2O

NH3

NH3

Br

OH2
H 2O

Cl

enantiomers

Cr(H2O)3BrClI
OH2
H2 O

H2O
OH2

Cr

Cl

H2 O

OH2

Cr

Br

Cl

Br

enantiomers

Cl
H2 O

Cr

OH2

I
H 2O

Br

Cr

OH2

Cl

Br

H2 O

OH2

Cr

Br

Cl

e.

OH2

OH2

OH2

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

N
N
Cl

Pt

2+

Cl

Pt

N
Cl

Cl

cis enantiomers

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2+

Cl
N
N

Pt
Cl

trans

N
N

Chapter 9 Coordination Chemistry I: Structures and Isomers

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

f.

N
Cl

NH3

H 3N

NH3

H3N

Cr

trans NH3 ligands

2+
2+

Br

2+

Pt

Cl

Cl

Cl

trans Cl ligands

[Pt(bipy)2BrCl]2+

Pt

H3N

NH3

NH3

Cr

NH3

enantiomers

Cl

Cr

Cl

Cl

Cl

Cl

Cr

g.

129

Br

Br

Cl

Cl

Pt

N
N

enantiomers

h.

Re(arphos)2Br2

Abbreviating the bidentate ligands As P :

Br
P
As

Re

Br
P

As

As

Re

Br

Br

Re

As

Br

Br

Br

Re

Re

P
As

As

As

As

As

As
Br

Br

Br

Br

Br

As

As

Re

As

As

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Re

P
As

P
As

Re
P

Br
Br

Br
Br

130

Chapter 9 Coordination Chemistry I: Structures and Isomers

i.

Re(dien)Br2Cl
Cl
N

Re

Br

Cl
Br

Br

Br

Br

Re

Br

Cl

Re

Cl

Br

Re

Br

9.13

Br

Cl

Re

Br

a. M(ABA)(CDC)
C
A

b. M(ABA)(CDE)
C
A
B

C
D

C
D

A
M

M
E

M
E

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C
D

C
D

C
D

C
D

Chapter 9 Coordination Chemistry I: Structures and Isomers

131

9.14
A

A
C
B

A
B

9.15

A
B

A
M

A
B

A
B

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
P
N

Ni

Cl
P

Ni

Cl

Cl

Ni

Cl

Cl

Cl

N
Cl

Ni

N
P

Ni

Cl

Cl

Cl

Cl

Ni

Ni

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Ni
P

Cl
Cl

Cl
Cl

132

9.16

Chapter 9 Coordination Chemistry I: Structures and Isomers

a, b.

Abbreviating the bidentate ligands N P and O S :

Cl
S
O

N
Cl
Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

N
P

P
N

Cl

Cl

Cl

Cl

Cl

Cl

Cl
Cl

Cl
Cl

9.17

The single CN stretching frequency indicates a trans

structure for the cyanides (the symmetric stretch of the
CN bonds is not IR active), while the two CO bonds
indicate a cis structure for the carbonyls (both the
symmetric and antisymmetric CO stretches are IR
active). As a result, the bromo ligands are also cis.

C
O

C
Br

Co
C
N

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C
Br

Chapter 9 Coordination Chemistry I: Structures and Isomers

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
P

As

Br

Br

OH2

H2O

N
P

As

As

Br

Br

NH3

H 3N

N
P

OH2
Br

H2O

Br

As

As

H3 N

NH3

Br

Br

As

H 2O

NH3

H3N

OH2

Br

Br

NH3

NH3

OH2

OH2

NH3

NH3

N
OH2

H2O

As

Br

As

1. Mo

2.

Mo

OH2

Cs

S
Mo

S
Mo

Mo

Cr
W

Mo

Mo

O
Cr

C1

Se

C1

O
S

Mo

Mo

Cr
W

Se

C1

O
Mo

Cr
W

Se

Se

Mo

C1

O
O

Mo

Cr

C1

Se

Cs

C1

Mo

Mo

Mo

Cr
Se

Mo

Mo

Mo

Mo

Se
Cr

O
Se

O
W

C1

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Mo
Cr

C1

M
OH2

S
Mo

N
Br

O
W

Mo

Mo

3.

Mo

N
Br

Mo

As

Cs C3v

S
Mo

d.

Mo

Mo

c.

As

Br

Br

b.

H3N

NH3

a, b.

As

OH2

OH2

9.22

NH3

20b 20c top ring: , bottom ring:

NH3

9.21

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

H2 O

Br

9.20

H3N

Br

a.

NH 3
OH2

OH2

9.19

As

OH2

Br

As

NH3

As

NH3

As

133

P
As

P
As

P
As

134

Chapter 9 Coordination Chemistry I: Structures and Isomers

S
Mo

Mo
Mo

Cr

9.23

Se
O

Mo
Se

W
O
O

Cs Cs

c.

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

Cr

The 19F doublet is from the two axial fluorines (split by the equatorial fluorine).
The 19F triplet is from the equatorial fluorine (split by the two axial fluorines).
The two doubly bonded oxygens are equatorial, as expected from VSEPR
considerations. Point group: C2v

9.24

F
O
O

Os

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] :

NCCuCN

NCCuCNCuCN

NCCuCNCuCNCuCN

[Cu2(CN)3] :
[Cu3(CN)4] :
+

[Cu2(CN)] :

CuCNCu

CuCNCuCNCu

CuCNCuNCCuCNCu

[Cu3(CN)2] :
[Cu4(CN)3] :

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
HC
chirality (C3 symmetry) and can be considered as similar to left-handed (PL) and
right-handed (PR) propellers. If two P(mesityl)3 phosphines are attached in a
linear arrangement to a gold atom, three isomers are possible:
3

PLAuPL

PRAuPR

PLAuPR

H 3C

mesityl

(PRAuPL is equivalent to PLAuPR, 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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CH3

Chapter 9 Coordination Chemistry I: Structures and Isomers

9.26

The point group is D3h. A representation based on the nine 1s orbitals

of the hydride ligands is:
D3h

A1
E
A2
E

E
9
1
2
1
2

2C3
0
1
1
1
1

3C2
1
1
0
1
0

2S3
0
1
1
1
1

h
3
1
2
1
2

3v
3
0
0
1
0

Re

z2
(x, y), (x2y2, xy)
z
(xz, yz)

135

= H

The representation reduces to 2 A1 + 2 E + A2 + ECollectively 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

O
Mn O
O
O

OO

OO

OO

OO

O Mn O
O
O
O
O

OO

OO

OO
O Mn O
O
O
O
O

O
O Mn
O

OO

O Cr O

O Cr O

O Cr O

NN

NN

NN

9.28

N
N

N
N
O
O

O
O

N
N

Co
O O

N
Co

O O

Co
O

O
O
N

N
N
O
O
N

Co

N
O

O
O

O O
N

Co
O O

N
Co

O
O
N

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136
9.29

9.30

Chapter 9 Coordination Chemistry I: Structures and Isomers

a.

Cu(acacCN)2: D2h

b.

C6

tpt: C2v

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

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,Ndiethylformamide 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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