Coeficientes de Selectividad Potenciometricos Cationes Inorg IUPAC 2000
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Chapter 9 Coordination Chemistry I: Structures and Isomers 123
Copyright © 2014 Pearson Education, Inc.
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.”)
124 Chapter 9 Coordination Chemistry I: Structures and Isomers
Copyright © 2014 Pearson Education, Inc.
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)
CoN O
N N
N
N
CoN
N
N
N
H
H2
4+
Chapter 9 Coordination Chemistry I: Structures and Isomers 125
Copyright © 2014 Pearson Education, Inc.
b. Diaquadiiododinitritopalladium(IV)
PdH2O ONO
ONO OH2
I
I
PdH2O ONO
ONO I
H2O
I
PdONO OH2
ONO OH2
I
I
PdH2O I
ONO OH2
I
ONO
PdONO ONO
H2O I
I
H2O
PdONOONO
OH2I
I
OH2
enantiomers c. Fe(dtc)3
FeS S
S S
S
S
FeSS
SS
S
S
S
SC
S
S
N
CH3
H
–
=
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.
126 Chapter 9 Coordination Chemistry I: Structures and Isomers
Copyright © 2014 Pearson Education, Inc.
9.8 a. triammineaquadichlorocobalt(III) chloride Isomers are of the cation:
CoH3N NH3
H3N Cl
H2O
Cl
CoH3N NH3
H3N OH2
Cl
Cl
+ +
CoCl NH3
H2O NH3
NH3
Cl
+
cis trans
mer fac
b. -oxo-bis(pentammine-chromium(III)) ion
CrO
H3N
H3N
H3N
H3N
NH3
CrO
NH3
H3N
NH3
NH3
NH3
4+
c. potassium diaquabis(oxalato)manganate(III) Isomers are of the anion:
MnH2O O
O O
O
H2O
MnOH2O
OO
O
OH2
MnO O
O O
H2O
H2O
cis enantiomers trans
– – –
9.9 a. cis-diamminebromochloroplatinum(II)
b. diaquadiiododinitritopalladium(IV) c. tri--carbonylbis(tricarbonyliron(0))
Pt
Cl NH3
Br NH3
PtONO OH2
H2O ONO
I
I
Fe Fe
C
C C
O
OOC C
C CC CO O
O
O O
O
Chapter 9 Coordination Chemistry I: Structures and Isomers 127
Copyright © 2014 Pearson Education, Inc.
9.10 9.11 M(AB)3
MB B
A A
B
A
MBB
AA
B
A
MA B
B A
A
B
MAB
BA
A
B
fac mer
9.12 a. [Pt(NH3)3Cl3]+
PtCl NH3
Cl NH3
NH3
Cl
PtNH3Cl
NH3H3N
Cl
Cl
+ +
fac mer
b. [Co(NH3)2(H2O)2Cl2]+
CoCl OH2
H2O NH3
NH3
Cl
CoNH3H2O
NH3H2O
Cl
Cl
+ +
CoCl OH2
Cl OH2
NH3
NH3
CoClH2O
OH2Cl
NH3
NH3
+ +
CoCl NH3
H2O NH3
OH2
Cl
CoClH3N
OH2H3N
H2O
Cl
+ +
enantiomers
H2N
CH2 C
O
O – = N O
MO O
N N
O
N
MOO
NN
O
N
MN O
O N
N
O
MNO
ON
N
O
fac mer
128 Chapter 9 Coordination Chemistry I: Structures and Isomers
Copyright © 2014 Pearson Education, Inc.
c. [Co(NH3)2(H2O)2BrCl]+
d. Cr(H2O)3BrClI
CrCl I
H2O OH2
OH2
Br
CrClI
OH2H2O
H2O
Br
enantiomers
CrH2O Br
I OH2
OH2
Cl
CrH2O Br
Cl OH2
OH2
I
CrH2O I
Cl OH2
OH2
Br e. [Pt(en)2Cl2]2+
PtCl N
N N
N
Cl
PtClN
NN
N
Cl
PtN N
N N
Cl
Cl
cis enantiomers trans
2+2+2+
CoH3N Cl
H3N Br
OH2
OH2
CoNH3H2O
NH3H2O
Cl
Br
+ +
CoCl OH2
Br OH2
NH3
NH3
CoBrH2O
OH2Cl
NH3
NH3
+ +
CoBr NH3
H2O NH3
OH2
Cl
CoBrH3N
OH2H3N
H2O
Cl
+ +
enantiomers
CoCl NH3
H2O NH3
OH2
Br
CoClH3N
OH2H3N
H2O
Br
+ +
enantiomers
Chapter 9 Coordination Chemistry I: Structures and Isomers 129
Copyright © 2014 Pearson Education, Inc.
f. [Cr(o-phen)(NH3)2Cl2]+
+ +
CrCl NH3
NH3
Clenantiomers
N
NCr
ClH3N
H3N
Cl
N
N
+
CrCl NH3
Cl
NH3
N
N
+
CrH3N Cl
NH3
Cl
N
N
trans Cl ligands trans NH3 ligands g. [Pt(bipy)2BrCl]2+
2+
PtCl
Br
enantiomers
N
N
N
NPt
Cl
Br
N
N
N
N
2+
2+
Pt
Br
N
N
Cl
N
N
h. Re(arphos)2Br2 Abbreviating the bidentate ligands As P:
ReBr AsBr As
P
P
ReBrAsBrAs
P
P
ReBr PBr P
As
As
ReBrPBrP
As
As
ReBr As
Br P
As
P
ReBrAs
BrP
As
P
ReAs As
P P
Br
Br
ReAs P
P As
Br
Br
130 Chapter 9 Coordination Chemistry I: Structures and Isomers
Copyright © 2014 Pearson Education, Inc.
i. Re(dien)Br2Cl
ReN Br
N Br
Cl
N
ReNBr
NBr
Cl
N
ReN Br
N Cl
Br
N
ReN N
N Cl
Br
Br
ReN N
N Br
Cl
Br 9.13 a. M(ABA)(CDC)
MD A
C B
A
C
MB AA D
C
C
MD AC A
B
C
MDACA
B
C
b. M(ABA)(CDE)
MD A
C B
A
E
MDA
CB
A
E
MB A
A D
C
E
MD A
C A
B
E
MDA
CA
B
E
MD B
C A
A
E
MDBCA
A
E
Chapter 9 Coordination Chemistry I: Structures and Isomers 131
Copyright © 2014 Pearson Education, Inc.
9.14
MB CA B
A
C
MBCAB
A
C
MB C
A B
A
C
MB BA A
C
C
MBBAA
C
C
MB AA C
B
C
MBBAC
B
C
MBC
AB
A
C
MB C
C B
A
A
MB C
A A
B
C
MBC
AA
B
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:
NiCl N
Cl N
P
P
NiClN
ClN
P
P
NiCl P
Cl P
N
N
NiClP
ClP
N
N
NiCl NCl P
N
P
NiClN
ClP
N
P
NiN N
P P
Cl
Cl
NiN P
P N
Cl
Cl
132 Chapter 9 Coordination Chemistry I: Structures and Isomers
Copyright © 2014 Pearson Education, Inc.
9.16 a, b. Abbreviating the bidentate ligands N P and O S:
MCl O
Cl P
N
S
MClO
ClP
N
S
MCl S
Cl P
N
O
MClS
ClP
N
O
MCl O
Cl N
P
S
MClO
ClN
P
S
MCl S
Cl N
P
O
MClS
ClN
P
O
MO NS P
Cl
Cl
MO P
S N
Cl
Cl
9.17 The single C–N stretching frequency indicates a trans
structure for the cyanides (the symmetric stretch of the C—N bonds is not IR active), while the two C–O bonds indicate a cis structure for the carbonyls (both the symmetric and antisymmetric C–O stretches are IR active). As a result, the bromo ligands are also cis.
CoBrBr
CC
C
C
O
N
O
N
–
Chapter 9 Coordination Chemistry I: Structures and Isomers 133
Copyright © 2014 Pearson Education, Inc.
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.
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:
9.22 a, b. 1. O
Mo S
MoMo
O W
OS
Mo O
MoMo
O W
O
Cs C3v
2. O
Mo S
MoMo
S W
OS
Mo O
MoMo
O W
S
Cs Cs
3. S
Cr O
MoMo
Se W
OO
Cr O
MoMo
Se W
SS
CrO
MoMo
SeW
OO
CrO
MoMo
SeW
S
C1 C1 C1 C1
Se
Cr O
MoMo
S W
OO
Cr O
MoMo
S W
SeSe
CrO
MoMo
SW
OO
CrO
MoMo
SW
Se
C1 C1 C1 C1
MOH2As
BrP
N
NH3
MBrAs
OH2P
N
NH3
MOH2As
NP
NH3
Br
MNH3As
BrP
N
OH2
MBrAs
NH3P
N
OH2
MNH3As
NP
OH2
Br
MOH2As
NH3P
N
Br
MNH3As
OH2P
N
Br
MBrAs
NP
OH2
NH3
MH2O As
Br P
N
NH3
MBr As
H2O P
N
NH3
MH2O As
N P
NH3
Br
MH3N As
Br P
N
OH2
MBr As
H3N P
N
OH2
MH3N As
N P
OH2
Br
MH2O As
H3N P
N
Br
MH3N As
H2O P
N
Br
MBr As
N P
OH2
NH3
134 Chapter 9 Coordination Chemistry I: Structures and Isomers
Copyright © 2014 Pearson Education, Inc.
S
Cr O
MoMo
O W
SeS
W O
MoMo
O Cr
Se
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). 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 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 right-handed (PR) propellers. If two P(mesityl)3 phosphines are attached in a linear arrangement to a gold atom, three isomers are possible:
PL—Au—PL PR—Au—PR PL—Au—PR
(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.
H3C
H3C
CH3
mesityl
Os
F
F
F
OO
+
Chapter 9 Coordination Chemistry I: Structures and Isomers 135
Copyright © 2014 Pearson Education, Inc.
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 3v 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)
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
9.28
Re
= H
CrO OOO
N N
OO O
OMnMn
CrO OOO
N N
OO O
O
CrO OOO
N N
OO O
OMnMn
CrO OOO
N N
OO O
O
CrO OOO
N N
OO O
OMnMn
CrO OOO
N N
OO O
O
Co
O O
OO
N
N
NN
N
N
N N
N
N
N
N
N
N
N
N
N
N
N
N
N
NN
N
N
N
Co
OO
OO
N
N
Co OO
OO
N
N
Co
OO
O O
N
N
Co
OO
OO
N
N
CoOO
OO
N
N
136 Chapter 9 Coordination Chemistry I: Structures and Isomers
Copyright © 2014 Pearson Education, Inc.
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, Mg2(dobdc) ) are significantly more effective at adsorbing carbon dioxide relative to adsorbing hydrogen. This is attributed, in part, to the higher polarizability of CO2 relative to that of H2. 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 CO2 adsorption capacity are MOF surface area and MOF accessible pore volume. As these values (tabulated below) increase, the CO2 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
Mg2(dobdc) 1800 0.573 The graphs in Figure 1 of the reference clearly indicate that Mg2(dobdc) adsorbs the most CO2
at 5 bar. The arrangement and concentration of open Mg2+ cation sites on the Mg2(dobdc) surface is hypothesized to render this MOF more susceptible to CO2 adsorption. This MOF, along with Cu-BTTri, which also features exposed metal sites, are identified as the best prospects for CO2 H2 separation.
9.31 The synthesis and application of amine-functionalized MOFs for CO2 adsorption is the general topic of the reference. While the M2(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 M2(dobdc) . One hypothesized solution was to prepare a MOF with the M2(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
O
O
O
O
dobpdc
dobdc
Chapter 9 Coordination Chemistry I: Structures and Isomers 137
Copyright © 2014 Pearson Education, Inc.
Amine-functionalized Mg2(dobpdc)was prepared by mixing H4(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 M2(dobpdc) collected by filtration after cooling. Dried samples of Mg2(dobpdc)were then heated for roughly one hour at 420 °C under dynamic vacuum. After this “activation” step, Mg2(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 Mg2(dobpdc) . The “activation” step was found necessary to completely remove residual N,N’-
diethylformamide from the Mg2+ 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.
HN
N
NH
N
COOHHOOC
HOOC COOH
The metallation options include premetallation and postmetallation. In premetallation, H4-TCPP-Cu and H4-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.