the chemistry of copper(ii) complexes in chemistry …
TRANSCRIPT
THE CHEMISTRY OF COPPER(II) COMPLEXES
by
MARK 0. SEIDLITZ, B.S.
A THESIS
IN
CHEMISTRY
Submitted to the Graduate Faculty of Texas Tech University in
Partial Fulfillment of the Requirements for
the Degree of
MASTER OF SCIENCE
Approved
May 1990
C/ V'
N 0 • '^'k ACKNOWLEDGEMENTS
I vish to express my sincere gratitude to Dr. Robert
Holverda for the many years of guidance and instruction
that have made this research possible. I vould also like
to thank my other committee members. Dr. Jerry Mills and
Dr. Bruce Whittlesey, for their understanding, advice, and
assistance throughout my graduate education.
I vould like to thank all the graduate students vho
have been friends to me throughout the past several years,
especially, Stephen Childress, Boyd Gafford, Woo-Yeong
Jeong, Joe McDonough, and Jesse Yeh.
Finally, I vould like to express thanks to my vife,
Elena, for her constant love and support vithout vhich
this vork vould not have been possible.
11
TABLE OF CONTENTS
ACKNOWLEDGEMENTS 11
ABSTRACT iv
LIST OF TABLES V
LIST OF FIGURES vii
I. INTRODUCTION 1
General Chemistry of Copper l
Objectives 3
II. EXPERIMENTAL PROCEDURE 9
Materials 9
Instruments 9
Syntheses 9
III. RESULTS AND DISCUSSION 14
IV. CONCLUSION 4 6
REFERENCES 47
iii
ABSTRACT
In this thesis vas discussed the successful syntheses
of the three nev compounds, bis(2-pyridylmethyl)2unineaqua-
copper(II) perchlorate, bis(pyridylmethyl)2uninepyridyl-
copper(II) perchlorate, and 2-[2-(2-pyridylethyl)-
iminomethyl]pyridinecopper(II) perchlorate.
Surprisingly, vith either vater or pyridine occupying
the fourth coordination position in the copper(II) dmpa
and pip complexes, no noticeable effect upon the d-d bands
vas detected in the UV/visible spectra.
An oxidized product, [CuLi(dmpa)(py)](ClO^)3, may
have been formed. If further vork proves this to be the
case, other non-hydroxylic oxidizing agents vill need to
be tried in an attempt to prepare [Cu(dmpa)(py)](ClO^)3.
It appears that basic H2O2 is too strong of an
oxidizing agent for the oxidation of [Cu(pip)(py)](C10^)2•
In the basic H2O2 media the pip ligand is vigorously
oxidized.
iv
LIST OF TABLES
1. UV/visible data for copper(III) complexes 6
2. Analytical data 21
3. IR data for the bis(2-pyridylmethyl)aunine- 23 (aqua) and (pyridyl)copper(II) complexes
4. IR bands and assignments for aqua and 2 4 pyridyl dmpa complexes
5. UV/visible data for the bis(2-pyridylmethyl) 27 amine(aqua)copper(II) complex
6. UV/visible data for the bis(2-pyridylmethyl) 28 amine(pyridine)copper(II) Complex
7. Comparison of UV/visible data for the aqua 29 and pyridyl bis(2-pyridylmethyl)-aminecopper(II) complexes in various solvents
8. UV/visible data for copper(II) complexes 30
9. IR data for the products of the attempted 33 oxidation of [Cu(dmpa)(py)](C10^)2
10. IR data for the pyridyl dmpa and attempted 34 oxidation product
11. IR data for the 2-[(2-(2-pyridyl)ethylimino)- 36 methyl]pyridine(aqua) and (pyridyl)copper(II) complexes
12. IR bands and assignments for aqua and pyridyl 37 pip complexes
13. UV/visible data for the 2-[(2-(2-pyridyl)- 40 ethylimino)methyl]pyridine(aqua)- and (pyridyl)copper(II) complexes
14. Comparison of the UV/visible data for the 41 bis(2-pyridylmethyl)amine(pyridyl)- and the 2-[(2-(2-pyridyl)ethylimino)methyl]pyridine-(pyridyl)copper(II) complexes
15. IR data for [Cu(pip)(py)](010^)2 and the 43 [Cu(pip)(py)](ClO^)3 attempt
16. IR data for three [Cu(pip)(py)](010^)2 45 oxidation side products
vi
LIST OF FIGURES
1. Energy levels of Cu(I), Cu(II), and Cu(III) 5 ions in various geometries
2. Structures of the bis(2-pyridylmethyl)- 7 amine(dmpa) and 2-[(2-(2-pyridyl)ethylimino)-methyl]pyridine(pip) ligands
3. Structures of the bis(2-pyridylmethyl)- 8 amine- and 2-[(2-(2-pyridyl)ethylimino)-methyl]pyridine-copper(II) complexes
4. IR spectra for [Cu(dmpa)(H2O)](C10^)2 22 and [Cu(dmpa)(py)](010^)2 compounds
5. UV/visible spectra of [Cu(dmpa)(H2O)]- 25 (010^)2 in various solvents
6. UV/visible spectra of [Cu(dmpa)(py)](ClO^)2 2 6 in various solvents
7. UV/visible spectra in various solvents for 31 [Cu(dmpa)(py)](010^)2 oxidation
8. IR spectra of [Cu(dmpa)(py)](010^)2 oxidation 32 product
9. IR spectra of [Cu(pip)(H2O)](010^)2 and 35 [Cu(pip)(py)](0104)2
10. UV/visible spectra for [Cu(pip)(H2O)](010^)2 38 in H2O
11. UV/visible spectra for [Cu(pip)(py)](ClO^)2 39 in HjO
12. IR spectra for [Cu(pip)(py)](010^)2 oxidation 42 and product #2312
13. IR spectra for product #2315 and #2321 4 4
Vll
r
CHAPTER I
INTRODUCTION
General Chemistry of Copper
Copper is a transition metal, vhich in the zero
oxidation state has an electron configuration of
[Ar]4s24p*3d'. Copper is found in three different
oxidation states: Cu(I), Cu(II), and Cu(III).
Copper(I) atoms have 10 d electrons, and if vieved to
be in an octahedral field, the d orbitals are filled, as
shovn in Figure l(a)^. Cu(I) complexes being d ^ have no
Jahn-Teller distortion. Cu(I) complexes are dieunagnetic
and typically colorless. If a Cu(I) complex is colored,
the color is a result of a charge transfer band or an
internal transition in a ligand.^
In the copper(II) oxidation state, the metal has 9 d
electrons. In a distorted octahedral field, the ordering
of the d orbitals is presented in Figure l(b)^. Jahn-
Teller distortion causes a splitting of e^ and t2g
orbitals.^'^ Most Cu(II) complexes are square planar for
this reason.^'^' Usually observed in the electronic
spectra of Cu(II) complexes is a single broad, poorly
resolved band envelope.^ This envelope is typical of
Cu(II) complexes in tetragonal complexes.^ These
complexes are generally blue or green because of an
absorption band in the 600-900 nm region of the spectrxim.
Copper(III) species have only 8 d electrons. The
expected ordering of the d orbitals is summarized in
Figure 1(c).^'^ Bonds to ligands on the z-axis are
greatly elongated, levering the energy of the system along
vith the symmetry.^ Because of this elongation along the
z-8ucis, those d orbitals vhich have a z-component vill be
stabilized relative to the other d orbitals. Cu(IlI)
complexes are usually square planar.^'^^ Square planar
complexes are favored by metal ions vith a d electron
configuration and ligands high in the spectrochemical
series.^^'^^ The expectation of square planar
coordination in Cu.(III) complexes has been confirmed by
X-ray crystallography.^^ In addition to other spectral
bands, spectra of Cu(III) complexes have at least one
intense charge-transfer band near 360 nm along vith the
concomitant Cu(II) spectral d-d band.^^'^^ Spectral data
for some knovn Cu(III) complexes are presented in
Table i.l4;i6,17,18,19,20
The structures of the tvo tridentate ligands used in
this study, bis(2-pyridylmethyl)amine, (dmpa) and 2-[(2-
(2-pyridyl)ethylimino)methyl]pyridine, (pip) are presented
in Figure 2. Dmpa contains tvo aromatic nitrogen atoms in
pyridyl groups and one aliphatic nitrogen atom.^^ The
second ligand used vas 2-[(2-(2-pyridyl)ethylimino)
methyl]pyridine, (pip). Pip also contains tvo aromatic
nitrogen atoms in pyridyl groups but instead of an
aliphatic nitrogen donor atom, it has one Schiff base
nitrogen.^^ The bis(2-pyridylmethyl)2unine, dmpa, and the
2-[(2-(2-pyridyl)ethylimino)methyl]pyridine, pip, ligands
vould be expected to form stable 1:1 complexes vith Cu(II)
and Cu(III) ions containing 5- and 6-membered chelate
rings (Figures 2 & 3).^^'^^'^^
The analytical methods used to characterize the
products formed are %C, H, & N elemental analyses, IR and
electronic spectroscopies.^^
Objectives
The primary objective of the synthetic and
spectroscopic studies presented in this thesis is to
advance the understanding of copper(II)-polyeunine complex
coordination chemistry. Of particular interest is the
relative positions of aliphatic euaine, aromatic zunine and
Schiff base nitrogen atoms in the spectrochemical series.
A secondary objective of this research vas to use tvo
tridentate nitrogen ligand-containing Cu(II) complexes in
an attempt to synthesize stable Cu(III) complexes by
reaction of these Cu(II) compounds vith basic hydrogen
peroxide. A related goal vas to determine vhether the
presence of a Schiff base linkage vould stabilize the
Cu(III) complexes.
Pree ion
3d
6a„
.M-r(
I I
'lODq
•WH-<'
<V-y^» ^19
d^,a ]SL
^xy • ^ig
\ dxz»dyr • ^g
t * ( %
* « * » *
0'
.
>
^ 1 ^ 1
0/?7
S
* * 122.
(a) ( b ) (c)
Figure 1
Energy levels of Cu(I), Cu(II), and Cu(III) ions in various geometries
T a b l e 1
U V / v i s i b l e d a t a f o r c o p p e r ( I I I ) c o m p l e x e s ^ ^
C u ( I I I ) Complex S o l v e n t U V / v i s i b l e Bands^
Cu( trans - t e tramine )^ ' ' ' ^* CH3CN 465 (ISOOO) 375 (12000)
275 (6700)
395 (14530) 335 (12690)
300 (2500)
310 (7800)
414 (12000)
560 (2400) 370 (26500)
KCu(3-Rbi)2*2H20 ^^ DMSO 270 (5000) 373 (8500) 490 Sh
* vavelength, nm; (molar absorptivity,M"^ cm"^)
Cu(trans-dien)^''" *
Cu(en)2^* ^
cu(gly)2"*' ^
Cu(I0g)2^" "
CuBr2(dtc) ^'
CH3CN
HjO
HjO
HjO
CH2CI2
C^"^ dmpa pip
Figure 2
Structures of the bis(2-pyridylmethyl)amine (dmpa) and 2-[(2-(2-pyridyl)ethylimino)methyl]
pyridine (pip) ligands
8
Cu (C104)2 (0104)2
X = a) H2O
b) pyridine
Figure 3
Structures of the bis(2-pyridylmethyl)2unine- and 2-[(2-(2-pyridyl)ethylimino)methyl]pyridine
copper (II) complexes
CHAPTER II
EXPERIMENTAL PROCEDURE
Materials
Reagent grade chemicals and solvents vere used
without further purification. The [Cu(pip)(H2O)](0104)2
complex vas synthesized by the literature method^^. All
of the elemental analyses reported vere obtained from
Desert Analytics (Tucson, Arizona).
Instruments
Infrared (IR) and UV/visible spectra vere obtained on
Perkin-Elmer 1600 Series FT-IR and Shimadzu UV-2 60
spectrophotometers, respectively. All pH measurements
vere taken at 25 ^C using a Metrohm/Brinkmann pH-104 pH
meter.
Syntheses
[Cu(dmpa)(H2O)](0104)2
A nev compound, [Cu(dmpa)(H2O)](0104)2/ ^^^
synthesized by adding 62.7757 g (0.1694 mol) of Cu(C104)2
to a beaker containing 50 mL of methanol, generating a
blue solution. To this solution 30.7 mL (0.1695 mol) of
10
bis(2-picolyl)amine vas added, affording a bright blue
precipitate. An additional 200 mL of methanol vas added,
and the reaction mixture vas stirred vith moderate heating
at 40 ®C for one hr. The solution vas then stirred
without heat and suction-filtered to obtain 71.9568 g
(0.1503 mol) of an air-dried bright blue precipitate,
[Cu(dmpa) (H2O) ] (0104)2/ * ** * blue-green supernatant. The
bright blue [Cu(dmpa)(H2O)](0104)2 precipitate vas then
vashed vith ethyl ether and vacuum dried. Yield: 89%
(72g, 0.15 mol). Anal. Calcd: %c 30.05; %H 3.15; %N 8.76.
Found: %C 30.77; %H 3.33, %N 8.61.
[Cu(dmpa)(py)](0104)2
The nev compound, [Cu(dmpa)(py)](0104)2/ ^^^
synthesized by transferring 36.3911 g (0.0760 mol) of
[Cu(dmpa)(H2O)](0104)2 ^^^^ ^ beaker containing 100 mL of
H2O, generating a murky bright blue solution. To this
solution vas added 6.2 mL (0.0766 mol) of pyridine, vhich
immediately turned the reaction mixture to a murky purple
color. Another 100 mL of H2O vas added to the reaction
mixture vhich vas stirred for 0.5 hr. and then cooled in
an ice bath. The reaction mixture vas suction-filtered to
obtain 37.5541 g (0.0696 mol) of a bright purple
11
precipitate, [Cu(dmpa)(py)](0104)2/ *^^ * clear deep blue
supernatant. The precipitate vas then vashed vith ethyl
ether and vacuum dried. Yield: 92% (38g, 7.0 mmol).
Anal. Calcd: %C 37.76; %H 3.35, %N 10.36. Found:
%C 37.30; %H 3.29; %N 10.12.
Attempted Synthesis of [Cu(dmpa)(py)](0104)3
The synthesis of the Cu(III) compound
[Cu(dmpa)(py)](0104)3 vas attempted by adding 19.1449 g
(0.0355 mol) of [Cu(dmpa)(py)](0104)2 into a beaker vith
5.7012 g (0.0355 mol) of LiC104*3H20, 0.2 mL of pyridine
(0.0025 mol), and 100 mL of H2O. The pyridine added vas
in a ten percent excess in order to make sure that H2O
vould not displace the pyridine as a ligand. Tventy-four
mL of 30% H2O2 vas added to the heated reaction mixture.
A reaction took place at 85 ^C, vith formation of a dark-
colored precipitate plus a dark green solution. The
solution vas cooled vith ice and suction-filtered to
obtain 14.4568 g of a gray precipitate vith a dark green
supernatant. The gray precipitate vas vashed vith ethyl
ether and vacuum dried. Anal. Calcd: %C 31.8; %H 2.68;
%N 8.75. Found: %C 37.34; %H 3.09; %N 10.07.
12
Synthesis of [Cu(pip)(py)](0104)2
[Cu(pip)(py)](0104)2 ^^3 synthesized by adding
2.0682 g (0.0042 mol) of [Cu(pip)(H2O)](0104)2 ^^ ^° ^^ ^^
methanol. The solution vas heated for 25 min. To this
solution 0.34 mL (4.2 mmol) of pyridine vas added along
vith 10 more mL of methanol, creating a dark blue-green
and cloudy solution. The reaction mixture vas heated
moderately, stirred, cooled, and suction-filtered to
obtain 1.3491 g (2.44 mmol) of [Cu(pip)(py)](0104)2/ a
pale blue precipitate vith a blue-green supernatant. The
precipitate vas vashed vith ethyl ether and vacuum dried.
Yield: 58% (1.3g, 2.44 mmol). Anal. Calcd: %C 39.11; %H
3.28; %N 10.13. Found: %C 38.71; %H 3.10; %N 10.24.
Attempted Synthesis of [Cu(pip)(py)](0104)3
The synthesis of [Cu(pip)(py)](0104)3 ^^^ attempted
by adding 5.8670 g (0.0119 mol) of [Cu(pip)(H2O)](CIO4)2
to 50 mL of H2O, generating a murky light green solution.
To this solution vas added 1.0 mL (0.0124 mol) of
pyridine, vhich immediately turned the solution to a dark
greenish-blue murky color. The ten percent excess of
pyridine vas to ensure that pyridine remains a ligand in
the fourth coordination position. The mixture vas then
stirred and 1.9087 g (0.0119 mol) of LiC104*3H20 vas
13
added. The reaction mixture vas placed in a vater bath at
80 °C, and 12 mL of 30% H2O2 solution vas added. An
immediate reaction occurred, as the reaction mixture
foamed and became a dark murky green color. The reaction
mixture remained in the vater bath for 45 min. This
solution vas alloved to cool and then placed in the
refrigerator overnight. The reaction mixture vas then
suction-filtered to obtain 0.1688 g of a greenish-brovn
precipitate and a dark green supernatant.
Attempted Synthesis of other [Cu(dmpa)(X)](0104)2 and [Cu(pip)(X)](0104)2 complexes
The syntheses of other [Cu(dmpa)(X)](0104)2 ^"^
[Cu(pip)(X)](0104)2 complexes vas attempted, X = NH3,
methyl amine, or benzyl amine, by the same method used in
the [Cu(dmpa)(py)](0104)2 and [Cu(pip)(py)](0104)2
syntheses above. Apparent copper(II)-aunine coordination
reactions vere signalled by distinct color changes
folloving the addition of these zunines. Precipitated
products vere shovn to be impure from the % C, H, and N
microanalysis results indicating that further purification
vould be necessary. These products vere not pursued
further in this thesis due to the desire to focus
upon the aqua and pyridyl copper(II) complexes of dmpa and
pip.
CHAPTER III
RESULTS AND DISCUSSION
Three nev copper(II) complexes vere synthesized:
[CU(pip)(py)](0104)2/ [CU(dmpa)(H2O)](0104)2/ and
[Cu(dmpa)(py)](0104)2* ^hese complexes vere characterized
by %C, H, & N microanalyses coupled vith infrared and
UV/visible spectroscopy.^^ The analytical data listed in
Table 2 for these three nev complexes confirms their
purities.
The infrared spectra for the nevly formed compounds,
[Cu(dmpa)(H2O)](0104)2 ^^^ [Cu(dmpa)(py)](0104)2/ can be
vieved in Figure 4. The IR band positions and assignments
for [Cu(dmpa)(H2O)](0104)2 ^^^ [Cu(dmpa)(py)](0104)2 can
be seen in Tables 3 and 4, respectively. A comparison of
the IR spectra for [Cu(dmpa)(H2O)](0104)2 ^^^
[Cu(dmpa)(py)](0104)2 reveals that the infrared band
frequencies increase slightly. An exception to these
findings is that one or both of the perchlorate bands in
the [Cu(dmpa)(py)](0104)2 complex are of a lover intensity
than those in the [Cu(dmpa)(H2O)](0104)2 complex.
The UV/visible spectra of [Cu(dmpa)(H2O)](CIO4)2 and
[Cu(dmpa)(py)](0104)2 ^^® presented in Figures 5 and 6 in
various solvents. The teUsulated d-d bands for the
14
I'
15
[CU(dmpa)(H2O)](0104)2 *^^ [Cu(dmpa)(py)](0104)2 complexes
in various solvents are in Tables 5 and 6, respectively.
It could be reasoneOsly expected that the
[Cu(dmpa)(py)](0104)2 complex vould have a d-d band vith a
larger 10 Dq than for [Cu(dmpa)(H2O)](0104)2/ because of
the relative positions of pyridine and H2O in the
spectrochemical series.^^ As a result, the d-d bands for
[Cu(dmpa)(py)](0104)2 should occur at a shorter vavelength
than for [Cu(dmpa)(H2O)](0104)2- ^^^Y small changes in
the vavelength of the d-d bands are observed betveen
[Cu(dmpa) (HjO)] (0104)2 *^^ [Cu(dmpa) (py) ] (0104)2 . '^^^^
indicates that the tridentate ligand, bis(2-
pyridylmethy1)amine, dmpa, is playing a significant role.
When the solvents are arranged in order of veakest field
ligand to strongest field ligand, as presented in Table 7,
the energy of the d-d bands increases correspondingly.
This vould seem to indicate that the solvent is playing an
important role. The presence of the broad band around 650
nm signals the presence of copper(II) in the complex vhich
is consistent vith the d-d bands characteristic of other
Cu(II) complexes, as presented in Table s.^^'^^'^^'^^
The UV/visible and IR spectra of the product produced
upon the addition of basic H2O2 to [Cu(dmpa)(py)](CIO4)2
are presented in Figures 7 and 8, respectively. The
analytical results in Table 2 represent that the %C, H,
16
and N analysis results for the attempted oxidation product
are very similar to those for the reactant
[Cu(dmpa)(py)](0104)2- ^^® ^^ ^^^^ positions and
assignments for [Cu(dmpa)(py)](0104)2 ^^^ ^^® desired
[Cu(dmpa)(py)](0104)3 complexes are tabulated in Tables 9
and 10, and reveal that the tvo products have very similar
IR bands. The UV/visible spectrum for the attempted
oxidation product of [Cu(dmpa)(py)](0104)2 ^^^ * ^'^ hand
in the visible region of the spectrum at 649.8 nm.
This band is shifted to a higher energy relative to
[Cu(dmpa)(py)](0104)2* ^^® attempted oxidation of
[Cu(dmpa)(py)](0104)2 to [Cu(dmpa)(py)](CIO4)3 does not
seem to have occurred as evidenced by elemental analysis,
IR, and UV spectroscopy. The product appears to be a
copper(II) species that is very similar to the precursor,
[Cu(dmpa)(py)](0104)2/ despite the distinct color change.
Another possibility, hovever, is that an oxidized
product vas formed, the [CuLi(dmpa)(py)](CIO4)3 complex.
A possible reaction pathvay for this is that H2O2 could
have been decomposed to hydroxyl radical. Hydroxyl ion
could then have been formed vith the addition of one
electron to the hydroxyl radical. Hydroxide ion is
capable of abstracting a proton from the aliphatic
nitrogen to form H2O. LiC104 is a source of Li*** vhich
could have then bonded to the aliphatic nitrogen. This
17
complex vould be expected to have spectroscopic properties
very similar to the [Cu(dmpa)(py)](0104)2 Precursor
complex. Due to insolubility problems, additional vork
beyond the scope of this thesis vill need to be done to
confirm vhether this is indeed vhat occurred.
The infrared spectra of [Cu(pip)(H2O)](0104)2 *^^ ^®
nevly formed [Cu(pip)(py)](0104)2 can be seen in Figure 9.
The IR band positions and assignments for these tvo
complexes are presented in Tables 11 and 12. A comparison
of the IR bands betveen [Cu(pip)(H2O)](0104)2 and
[Cu(pip)(py)](0104)2 ^®v®als that the IR spectra are very
similar vith the addition of a fev secondary/aromatic
amine stretches in the [Cu(pip)(py)](0104)2 complex. This
result is to be expected vith the additional pyridyl group
for this complex.
The UV/visible spectra of [Cu(pip)(H2O)](0104)2 and
[Cu(pip)(py)](0104)2 complexes in H2O can be seen in
Figures 10 and 11, respectively. The tabulated UV/visible
bands for [Cu(pip)(H2O)](0104)2 ^^^ [Cu(pip)(py)](CIO4)2
are presented in Table 13. There is only a slight shift
in the vavelengths of the d-d bands for
[Cu(pip)(H2O)](0104)2 and [Cu(pip)(py)](0104)2 in pH 3.18
and 10.30 solutions. The UV bands occurring near 380 nm
in the [Cu (pip) (H2O) ] (0104)2 * * [Cu(pip) (py) ] (0104)2
18
complexes are believed to be due to internal ligand
transitions.27/28
The d-d bands in the visible spectra of the
[Cu(dmpa)(py)](0104)2 *^^ [Cu(pip)(py)](0104)2 complexes
are presented in Table 14. It is observed that in the
high and lov pH solutions of [Cu(dmpa)(py)](0104)2 and
[Cu(pip)(py)](0104)2/ ^^^ ^"^ ^^^^ ^^ *^®
[Cu(pip)(py)](0104)2 complex occurs at a longer vavelength
than the [Cu(dmpa)(py)](CIO4) complex and thus a lover
energy than in the [Cu(dmpa)(py)](CIO4) complex. Also,
the molar adssorptivity in both the pip complexes is lover
than in the analogous dmpa complexes.
The IR spectrum of the desired [Cu(pip)(py)](CIO4)2
oxidation product is presented in Figure 12. A comparison
of the IR positions and assignments for the desired
[Cu(pip)(py)](0104)2 oxidation and [Cu(pip)(py)](CIO4)2
complexes can be vieved in TzUsle 15. The
Cu(pip)(py)](0104)2 oxidation product and the
Cu(pip)(py)](0104)2 complex have IR bands vhich are
considerably different. The product formed in the
oxidation attempt is not soluble in H2O (pH 5.3), CH3CN,
or n-hexane, and relatively insoluble in CH3OH. Only some
of the product goes into solution in CH3OH. The soluble
part generates no d-d band in the visible region of the
spectrum. The UV spectrum of the [Cu(pip)(py)](CIO4)2
19
methanolic solution contains tvo bands at 257.0 nm and
204.2 nm, probably pyridyl internal transitions.^7/28
In the [Cu(dmpa)(py)](0104)2 oxidation, the product
formed after the oxidation vas the major product. This
vas not so in the [Cu(pip)(py)](0104)2 reaction. During
the oxidation of [Cu(pip)(py)](0104)2/ several products
vere isolated. None of these products occurred in an
appreciable yield. Side products #2312, 2315, and 2321
vere present in the original supernatant solution and
appeared to differ only in their solubilities in the
methanol/ethyl ether solvent. These side products vere
isolated upon successive cycles of evaporation, methanolic
dissolution and precipitation vith the addition of a
minimal zunount of ethyl ether. The side products #2312,
2315, and 2321 demonstrated a dramatic change in
solubility properties relative to the [Cu(pip)(py)](CIO4)2
complex. Once the side products vere separated by
precipitation, they vere no longer soluble in that
solution.
The IR spectra for side products #2312, 2315, and
2321 are displayed in Figures 12 and 13. In Table 16, the
infrared band assignments and positions for the three
major side products #2312, 2315, and 2321 are presented.
Product #2312 does not appear to contain any pyridyl
groups. The attempted oxidation product and product #2321
20
appear to be quite similar to each other. The attempted
oxidation products and the other three side products
appear to have significantly less IR bands than the
precursor, [Cu(pip)(py)](0104)2* ^^ additional band
appears near 1600 cm'^ for products #2315, 2321, and the
first isolated [Cu(pip)(py)](0104)2 oxidation product.
This peak is possibly due to the presence of C02* The CO2
peak could be -l-a result of the basic H2O2 medium oxidizing
the pip ligand.
The oxidation of [Cu(pip)(py)](0104)2 does not seem
to have occurred vhen taking into account the lack of a
visible band, the significantly different solubility
properties, and the severely differing IR bands from the
[Cu(pip)(py)](0104)2 complex. The [Cu(pip)(py)](CIO4)2
oxidation product vas not sent out for analysis as there
vere several minor side products generated.
Table 2
Analytical data
21
Complex Observed Percentage Calculated Percentage
%C %H %N %C %H %N
[Cu(dmpa)(HjO)](010^)2
[Cu(dmpa)(py)](010^)2
[Cu(dnpa)(py)](ClO^)3
[Cu(pip)(py)](010^)2
[Cu(pip)(H20)](C10^)2*
3 0 . 7 7
3 7 . 3 0
3 1 . 3 4
3 8 . 7 1
3 . 3 3
3 . 2 9
2 . 6 4
3 . 1 0
8 . 6 1
1 0 . 1 2
8 . 6 0
1 0 . 2 4
3 0 . 0 5
3 7 . 7 6
3 7 . 3 4
3 9 . 1 1
3 . 1 5
3 . 3 5
3 . 0 9
3 . 2 8
8 . 7 6
1 0 . 3 6
1 0 . 0 7
1 0 . 1 3
^ prepared by the literature method^^
22
•.•7-V
[Cu(dnpa)(HjO)](0104)2
O.ltJ, r 1 1 1 I I I r — — aooa 3000 ISM MO. IMO IMO SOO 0 »-<
[ C u ( d m p a ) ( p y ) J ( C l O ^ j j
Figure 4
IR spectra for [Cu(dmpa)(H2O)](010^)2 and [Cu(dmpa)(py)](0104)2 compounds
23
Table 3
IR data for the bis(2-pyridylmethyl)aminefaqua) and (pyridyl) copper(II) complexes^''^
Complex IR Data
[Cu(dmpa)(H2O)](010^)2
3854.5 w, 1609.4 S, 1449.2 m, 1143.7 VS, 1028.1 m,
7 2 6 . 5 V , 4 2 1 . 0 w
3 4 4 8 . 1 b / s , 1 5 7 7 . 8 W°,
4 0 0 . 0 V, 1 1 2 0 . 9 V S ,
9 4 0 . 7 y.
2364.0 V, 1560.2 w, 1282.4 m, 1090.9 VS, 778.6 W,
636.0 Sh/m, 627.6 S
[Cu(dmpa)(py)](010^)2
3854.3 m, 3074.8 m, 1609.9 VS, 1542.4 w, 1400.0 W,
1286.0 m.
3448.1 b/m, 2346.0 W, 1571.5 w, 1480.1 m, 1350.1 w,
1250.0 w. 1108.8 b/VS, 1031.9 sh/VS, 967.6 W, 902.0 W, 768.3 S,
701.1 S, 422.9 m
942.3 m, 815.9 W, 759.1 m,
623.3 VS,
3239.1 s, 2028.0 V, 1560.2 V, 1452.1 VS, 1309.2 w, •
1 2 2 4 . 0 m, 1 0 0 2 . 6 m, 9 3 0 . 0 m, 7 8 0 . 8 m, 7 2 8 . 6 W,
4 9 6 . 2 w .
^ Infrared Spectra in KBr Pellet (cm~^)
^ sh: shoulder vs; very strong s: strong m; medium v: veak b: broad
^ found in data table from IR spectra but cannot clearly make out peak on spectra
Table 4
IR bands and assignments for a(Tua and pyridyl dmpa complexes*'^
24
[Cu(diBpa) (X)] (0104)2
l°,20,3« uiin«s (1250-1020)(C-H),^, (uncoBj. C-M)
AroB. aaines C-N (1342-1266)
2^ aroa. aaines (13S0-1280)
3^ aroa. aaina (1360-1310)
(a)
X s-
2° or 3° aainas -CH.-M- (d, CH2(sciss) (1474-1445)
RCHsNR CsN (S) (1689-1471)
pyr C-H (S) (3077-3003)
pyridina M-H (a) (3500-3220)
ring vibrs. (s) (1600-1300)
aroa. C-H (s) (3080-3010)
C-C, C-M (S) (1600-1430)
py gaaaa C-H (781-740)
CIO." (1050-1150 620-640)
cm
t
HjO
1120.9 VS 1028.1 a 1090.9 VS
1282.4 a
1282.4 a
no
1449.2 S
1609.4 S 1560.2 W 1479.0 a
no
3448.1 b/S no
1449.2 a
no
1449.2 a
778.6 a
1120.9 VS 627.6 •
py
1108.8 b/VS 1031.9 Sh/vs 1250.0 W,
1286.0 a 1309.2 w
1286.0 a 1350.1 W,
1309.2 W
1452.1 VS
1609.9 VS 1560.2 W 1480.1 a.
3074.8 a
3448.1 b/B 3239.1 S
1452.1 VS
3074.8 a
1452.1 VS
780.8 a.
1108.8 b/VS 62 3.3 VS
1224.0
1309.2
1571.5 1542.4
768.3 759.1
a
w
w
a
^ sh: shoulder vs: very strong m: medium v: veak b: broad
s: strong
25
3S$
(•) (b)
» Ui O O
/'
/
\ "
\
(e) (d)
!a) in H,0; (b) in CH3CH; (c) in CH3OH; (d) in pyridin.
Figure 5
UV/visible spectra of [Cu(dmpa)(H2O)](CIO4)2 in various solvents
26
8 %
(c) (d)
,) in PH 3.18 HjO; (b) in pH 10.3 HjO, (c) in CM3OH; (d) in pyridine
Figure 6
UV/visible spectra of [Cu(dmpa)(py)](CIO4)2 in various solvents
27
Table 5
UV/visible data for the bis(2-pyridylmethyl) amine(aqua)copper(II) complex^
[Cu(dmpa)(HjO)](0104)3
Water
6 5 2 . 0 2 5 3 . 0 1 9 3 . 2
pH 3.18
(15337) (39526) (51760)
Methanol
659.2 253.8 204.4
(15170) (39401) (48924)
Acetonitrile
6 0 5 . 4 2 5 4 . 0 1 9 3 . 8
(16518) (39370) (51600)
((89.35)) ((9651)) ((24660))
((86.48)) ((10130)) ((16310))
((120.8)) ((13510)) ((23330))
pH 10.30
653.0 254.2 194.4
(15314) (39339) (51440)
Pyridine
616.8 311 sh
(16213) (32154)
((89.09)) ((9702))
((27620))
((148.4)) ((1496))
vavelength maximxim, nm; ((molar absorptivity))
(vavenumber. cm"^);
28
Table 6
UV/visible data for the bis(2-pyridylmethyl) amine(pyridine)copper(II) complex^
[Cu(dmpa)(py)](0104)3
Water pH 3.18
652.0 254.8 193.8
(15337) (39246) (51600)
Methanol
660.0 256.4 204.0
(15152) (39002) (49020)
Acetonitrile 600.2 (16661)
( ( 9 1 . 7 0 ) ) ( ( 1 5 5 3 0 ) ) ( ( 2 6 9 3 0 ) )
( ( 8 3 . 7 1 ) ) ( ( 1 2 0 4 0 ) ) ( ( 1 7 7 1 0 ) )
( ( 1 3 1 . 5 ) )
pH 1 0 . 3 0
6 4 8 . 4 2 5 6 . 0 1 9 3 . 8
(15423) (39063) (51600)
((91.43)) ((12150)) ((36660))
Pyridine
618.8 (16160) ((149.9))
^ vavelength maximum; nm ((molar absorptivity))
(vavenumber, cm-1)
29
Table 7
Comparison of UV/visible data for the aqua and pyridyl bis(2-pyridylmethyl)aminecopper(II) complexes
in various solvents^
Solvent
CH3OH < H-0 < Pyridine < CH3CN
[Cu(dmpa)(HjO)](0104)2 ^^9-2 653.0 616.8
[Cu(dmpa)(py)](0104)2 ^60.2 648.4 618.8
605.4
600.2
vavelength maximum, nm
30
Table 8
UV/vis ib le data for copper(II) complexes
Complex U V / v i s i b l e Bands^
[ C u ( t e p a ) C l ] P F g 24 555 J200) 967 sh (48)
[Cu(tmpa)Cl]PP5 2* 962 (210) 632 sh (88)
CU(TPA)(0104)2 ^* 872 (214) 985 sh (162)
CU(TLA)(0104)2 ^* «95 (130) 800 sh (110)
CU(TPEN)(0104)2 2^ fi92 (175) 886 sh (75)
Cu(p ip) (N03)2*H20 2"' 668 (55) 379 (50)
C u ( p i p ) ( N 0 3 ) 2 ^^ ««8 <56) 379 (70)
[ C u ( p i p ) ] ( i m ) (N03)3*2.5H20 27 637 (68) 377 (68)
[Cu(PMDT)]2( im)(0104)3 27 643 (196)
[Cu(PMDT)]2(2-Meim) ( 0 1 0 4 ) 3 27 **" ^"*^
cu(pdahx) ( 0 1 0 4 ) 2 " ^ «03 < " 2 )
Cu(pdahp) (010^)2 ^* ^ «03 (143)
C u ( p d a o ) ( 0 1 0 4 ) 2 ^* ^ 589 (245)
O u ( p d a n ) ( 0 1 0 4 ) 2 26 b 659 (274)
* wavelength, nm; (molar absorptivity,M'^ cm" )
^ in a H2O solution
31
(a) (b>
8 S
(c) <d)
(a) in HjO; (b) in CH3OH; (c) in CR3CM; (d) in pyridine
Figure 7
UV/visible spectra in various solvents for [Cu(dmpa)(py)](0104)2 oxidation
32
3S00 3000 asoo tooo ca- soo
Figure 8
IR spectra of [Cu(dmpa)(py)](0104)2 oxidation product
33
Table 9
IR data for the products of the attempted oxidation Of [Cu(dmpa)(py)](0104)2
[Cia(dBpa) (py)] (010^)3 Attempt
3442.0 b/B, 2938.0 V, 2030.0 w, 1489.7 a, 1383.3 W,
3239.3 a, 2360.6 V, 1610.1 S, 1481.4 a, 1351.4 W,
3076.1 a 2339.9 W 1573.6 a, 1451.8 s, 1309.4 W,
1286.1 a, 1249.8 w, 1223.6 a, 1200.5 w, 1102.2 VS, 1057.3 sh/vs, 1031.6 sh/a, 1003.3 ah/a, 967.2 a, 942.9 a, 929.6 a, 901.9 W, 815.8 W, 780.8 ah/a, 767.6 a.
759.8 ah/a, 655.6 w, 496.2 W, 423.4 a
729.1 W, 700.8 a, 645.7 ah/w, 622.1 a, 484.8 W, 460.0 ah/v.
(Cu(pip)(py)1(0104)3 Attempt
12312
#2315
38S4.4 a, 1399.9 a, 1108.6 a, 695.7 w,
3854.4 a, 2345.5 a, 800.2 a.
2345.9 w, 1362.6 a, 820.7 a, 626.5 a,
3448.1 a, 1400.0 a, 670.1 W,
1654.3 V9, 1318.8 a, 764.0 V, 504.8 a
2366.5 a, 1090.2 va, 463.2 a
12321
3854.4 1654.3 1458.4 1400.0
3854.4 1654.2 1121.4 695.5 428.1
VS, va. a. a.
w# va. a. w# w
3448.1 VS, 1508.2 a. 1438.1 a. 1121.5 S,
3422.1 b/S, 1362.3 a. 820.9 a, 624.5 W,
2346.1 W, 1466.1 a. 1420.1 a. 625.5 W
2346.1 W, 1318.8 a. 765.2 W, 505.6 a
^ Infrared Spectra in KBr Pellet (cm~^)
sh: shoulder vs: very strong s: strong m: medium w: weaX b: broad
Table 10
IR data for the pyridyl dmpa and attempted oxidation product^'^
34
l<>,2<>,3<' a a i n e s (1250-1020) (C-M^Y) ( u n c o n j . C-M)
Aroa. a a i n e s C-M (1342-1266)
2^ a r o a . amines (1350-1280)
(s)
3** a r o a . ( 1 3 C 0 - 1 3 1 0 )
l i n e
o r 3^ a a i n e s -CH,-M-( d , C H 2 ( s c i s a ) ( 1 4 7 4 - 1 4 4 5 )
RCHsMR CsM ( a ) ( 1 6 8 9 - 1 4 7 1 )
pyr C-H ( s ) (3077-3003)
p y r i d i n e M-H ( s ) ( 3 5 0 0 - 3 2 2 0 )
r i n g v i b r s . ( s ) ( lCOO-1300)
a r o a . C-H ( s ) ( 3 0 8 0 - 3 0 1 0 )
C - C , C-M ( s ) ( 1 6 0 0 - 1 4 3 0 )
py gaama C-K ( 7 8 1 - 7 4 0 )
1 1 0 8 . 8 b /VS 1 0 3 1 . 9 s h / v a 1 2 5 0 . 0 V 1 2 2 4 . 0 a
1 2 8 6 . 0 a 1 3 0 9 . 2 V
1 2 8 6 . 0 a 1 3 5 0 . 1 W 1 3 0 9 . 2 w
1 3 0 9 . 2 W
1 4 5 2 . 1 v a
1 4 5 2 . 1 va
7 8 0 . 8 a 7 6 8 . 3 a 7 5 9 . 1 a
1102.2 va 1031.6 ah/a 1249.8 V 1223.6 a,
1286.1 a 1309.4 w
1286.1 a 1351.4 W 1309.4 W
1 3 5 1 . 4 W
1 4 5 1 . 8 a
1609.9 1480.1 1571.5 1560.2 1542.4
3074.8
3448.1 3239.1
1452.1
3074.8
va a w w w
a
b/a a
va
a
1610.1 1481.4 1573.6 1489.7 1451.8
3076.1
3442.0 3239.3
1451.8
3076.1
a a a a a
a
b/ a
s
a
1 4 5 1 . 8 a
7 8 0 . 8 a h / I 7 6 7 . 7 a 7 5 9 . 8 ah / I
1 2 0 0 . 5 W, 1 0 5 7 . 3 S h / v s
CIO." (1050-1150 & (620-640)
1108.8 b/VS 623.3 VS
1102.2 VS 622.1 S 1057.3 Sh/vs
* cm-1
^ sh: shoulder vs: very strong m: medium v: weaX b: broad
s: strong
35
ED
11.19-
2000 laae I M O ur> soo
[Cu(pip)(HjO)1(0104)2
O
[ C u ( p i p ) ( p y ) l ( 0 1 0 ^ ) 2
Figure 9
IR s p e c t r a of [Cu(pip)(H2O)](0104)2 and [ C u ( p i p ) ( p y ) ] ( 0 1 0 4 ) 2
36
Table 11
IR data for the 2-[(2-(2-pyridyl)ethylimino) methyl]pyridine(aqua) and (pyridyl)
copper(II) complexes ^'^
[Cu(pip)(H20) 1(0104)2
[Cu(pip)(py)1(0104)2
3854.3 1654.3 1604.1 1223.4 1088.3
3854.6 1654.3 1560.3 1378.6 1143.9
1024.0 636.3 i 507.6
m. m. s. m. VS,
3, m. m. B# VS,
m sh/s w.
3422.0 1647.9 1560.2 1143.9 775.9
3489.5 1648.0 1482.4 1304.1 1112.4
770.2 , 627.7 426.0
b/S, m. m. VS, m.
b/S m. m. m. VS,
s. 3, w
2345.8 1637.1 1442.5 1116.0 626.2
2345.7 1604.4 1443.2 1224.6 1091.2
700.2 595.9
w. m. m. V S , s
m. 3, 3, m. V S ,
m. w.
^ Infrared Spectra in KBr Pellet (cm~^)
^ sh: shoulder vs: very strong s: strong m: medium v: vea)c b: broad
Table 12
IR bands and assignments for agua and pyridyl pip complexes*'"
37
1^,2°,3° amines (1250-1020)(C-N) (uneoQJ. C-N)
(V)
Axom. amines C-N (s) (1342-1266)
2^ arom. amines (1350-1280)
RCH=NR C=N (s) (1689-1471)
pyridine N-H (s) (3500-3220)
ring vibrs. (s) (1600-1300)
C-C, C-N (s) (1600-1430)
py gamma C-H (781-740)
ClO, (1050-1150 6 620-640)
HjO
1223.4 1143.9 1088.3
no
m VS
vs
py
1224.6 1143.9 1091.2
1304.1
ffl
vs VS
m
no
1654.3 m 1647.9 m 1604.1 s 1560.2 m
3422.0 b/S
1560.2 m 1442.5 m
1560.2 m
775.9 m
1116.0 VS 626.2 S
1304.1 m
1654.3 m 1648.0 m 1604.4 S 1560.3 m,
3489.5 b/S
1482.4 m
1560.3 1443.2 1482.4 1378.6 1304.1
m s m m m
1560,
779
1112 627
.3
.2
.4
.7
m
s
vs s
-1 * Infrared Spectra in KBr Pellet (cm *)
^ sh: shoulder vs: very strong s: strong m: medium w: wea)c b: broad
38
< e A w
(b)
(a ) i n pH 3 . 1 8 H2O; (b) i n pH 1 0 . 3 0 HjO
Figure 10
UV/visible spectra for [Cu(pip)(H2O)](0104)2
in H2O
39
(b )
(a) in pH 3 . 1 8 HjO; (b) i n pH 1 0 . 3 0 HjO
Figure 11
UV/visible spectra for [Cu(pip)(py)](0104)2
in H2O
40
Table 13
UV/visible data for the 2-[(2-(2-pyridyl) ethylimino)methyl]pyridine(aqua)- and
(pyridyl)copper(II) complexes*
[Cu(pip)(HjO)](0104)2
Water pH 3.18
668.2 394.8 296.4
287.6 259.0 202.0
(14966) (25329) (33738)
(34771) (38610) (49505)
((38.21)) ((100.8)) ((4983))
((6160)) ((8375)) ((20790))
pH 10.30
665.2 364 Sh 288.6
258.6 199.2
(15038) (27473) (34650)
((56.37)) ((103.4)) ((7989))
(38670) ((9254)) (50201) ((29600))
[Cu(pip)(py)](0104)2
Water pH 3.18
668.0 373.2 296.4
287.6 256.0 202.0
(14970) (26795) (33738)
(34771) (39063) (49505)
((50.67)) ((50.67)) ((6013))
((7448)) ((14560)) ((27150))
pH 10.30
661.4 (15119) ((56.43)) 372 Sh (26882) ((51.14)) 289.0 (34602) ((9248))
2 5 6 . 6 2 5 0 . 6 1 9 8 . 4
( 3 8 9 7 1 ) ( 3 9 9 0 4 ) ( 5 0 4 0 3 )
( ( 1 2 7 2 0 ) ) ( ( 1 2 6 4 0 ) ) ( ( 3 8 1 4 0 ) )
^ wavelength mzucimum, nm; ((molar absorptivity))
(wavenumber. cm"^);
41
Table 14
Comparison of the UV/visible data for the bis(2-pyridylmethyl)amine(pyridyl)- and the 2-[(2-(2-pyridyl)ethylimino)methyl]pyridine(pyridyl)-
copper(II) complexes^
[Cu(pip)(py)](0104)2 [Cu(dmpa)(py)](0104)2
Water
pH 3.18 668.0 (14970) ((50.67)) 652.0 (15337) ((91.70)) pH 10.30 661.4 (15119) ((56.43)) 648.4 (15423) ((91.43))
^ wavelength maximum, nm; (wavenumber, cm~^) ; ((molar absorptivity))
».m-IT
4.i4Jr I I I r
([Cu(pip)(py)](ClO^jj oxidat ion
42
loee 900 0
o 17.ai f t
jky----^^--^^
l.tt-V— r 1 1 r— 40(0 3B00 3000 3900 2040
— I -.900 ICOO 900 0 ca"
Product #2312
Figure 12
IR spectra for [Cu(pip)(py)](0104)2 oxidat ion and product #2312
43
Table 15
IR data for [Cu(pip)(py)](0104)3 ^^S [Cu(pip)(py)](0104)3 attempt*'^
d the
Icu(pip)(x)j(cio^)j
l',2'',3" aainas <C-M(^. (uacoBj (12Sd-i020)
Aroa. aainoa c-M (1342-12CC)
2** aroa. aainas (1350-1280)
3® aroa. aaiaa (1380-1310)
Z s
C-M)
(a)
a" or 3® aaiaas -CH2-M-(d, Ca2(aoisa) (1474-1445)
RCHsNR CsM (a) (1889-1471)
py C-H (a) (3077-3003)
pyridiaa M-H (a) (3S00-3220)
riB9 Tibra. (a) (1800-1300)
aroa. C-H (a) (3080-3010)
C-C, C-M (a) (1800-1430)
py gaaaa C-H (781-740)
CIO." (1050-1150 (820-840)
8
py
1112.4 1143.9 1224.8 1091.2 1024.0
1304.1
1304.1
no
no
1654.3 1848.0 1604.4 1560.3 1482.4
no
3489.S
1378.8 1304.1 1443.2 1580.3 1482.4
no
1580.3
779.2
1112.4 827.7
1143.9 838.3
ox
vs 1108.8 S va • vs a
a 1318.8 •
a 1318.8 •
1318.8 •
no
• 1854.3 vs
no
b/s 3422.2 s
a 1399.9 a a 1382.6 s a 1318.8 a a a
no
a no
S 764.0 w
va 1108.6 s a 628.5 • va ah/a
cm
^ sh: shoulder m: medium w:
vs: very strong s: strong weaX b: broad
44
O
Product «2315
O
>.»+- MOO 9B00 I I I I
1000 lOOO tooo 900
• »
Product #2321
Figure 13
IR spectra for products #2315 and #2321
Table 16
IR data for three [Cu(pip)(py)J (0104)2 oxidation side products*'*'
45
1<»,2^,30 aminaa (C-M4^J (unconj. C-H) (1250-1020)
Aroa. aainas C-N (a) (1342-1266)
2^ arom. aminos (1350-1280)
3** arom. amino (1360-1310)
2« or 3« inas -CHj-l (d. CH2(sciss) (1474-1445)
RCH=NR C=N (S) (1689-1471)
py C-H (S) (3077-3003)
pyridina N-H (s) (3500-3220)
ring vibr^. (s) (1600-1300)
arom. C-H (s) (3080-3010)
C-C, C-N (S) (1600-1430)
py gamma C-H (781-740)
CIO4" (1050-1150 « 620-640)
*2312
1090.2
no
no
no
no
VS
#2315
1121.5 s
no
no
no
1466.1 m 1458.4 a
12321
1121.4 a
1318.8 a
1318.8 a
1318.8 a
no
no
no
3448.1 a
1400.0 S
no
no
no
1654.3 vs 1654.2 vs
no no
3448.1 vs 3422.1 b/S
1400.0 a 1466.1 a 1458.4 a 1438.1 a 1420.1 a
no
1466.1 a 1458.4 a 1438.1 a
no
1362.3 S 1318.8 a
no
no
765.2 w
1090.2 VS 1121.5 s 1121.4 a 625.5 V 624.5 w
• Infrared Spectra in KBr Pellet (cm"^)
^ sh: shoulder vs: very strong s: strong m: medium w: weaX b: broad
CHAPTER IV
CONCLUSION
In this thesis was discussed the successful syntheses
of the three new compounds, bis(2-pyridylmethyl)sunineaqua-
copper(II) perchlorate, bis(pyridylmethyl)aminepyridyl-
copper(II) perchlorate, and 2-[2-(2-pyridylethyl)-
iminomethyl]pyridinecopper(II) perchlorate.
Surprisingly, with either water or pyridine occupying
the fourth coordination position in the copper(II) dmpa
and pip complexes, no noticeaJsle effect upon the d-d bands
was detected in the UV/visible spectra.
An oxidized product, [CuLi(dmpa)(py)](OIO4)3, may
have been formed. If further work proves this to be the
case, other non-hydroxylic oxidizing agents will need to
be tried in an attempt to prepare [Cu(dmpa)(py)](CIO4)3.
It appears that basic H2O2 is too strong of an
oxidizing agent for the oxidation of [Cu(pip)(py)](0104)2•
In the basic H2O2 media the pip ligand is vigorously
oxidized.
46
REFERENCES
1.
2.
3.
Lever, A.B.P., "Inorganic Electronic Spectroscopy**; 2nd ed.; Elsevier: New York, 1984; pg. 26.
Cotton, p.A.; Wilkinson, G., ''Advanced Inorganic Chemistry**; 4th ed.; Wiley-Interscience: New York, 1980; pg. 800.
Cotton, F.A.; Wilkinson, G., •*Advanced Inorganic Chemistry"; 4th ed.; Wiley-Interscience: New York, 1980; pg. 811.
Huheey, J.E., **Inorganic Chemistry**; 3rd ed.; Harper & Row: New York, 1983; pp. 407-411.
Huheey, J.E., ••Inorganic Chemistry**; 3rd ed.; Harper & Row: New York, 1983; pg. 410.
Lever, A.B.P., •*Inorganic Electronic Spectroscopy**; 2nd ed.; Elsevier: New York, 1984; pg. 356.
Lever, A.B.P., ••Inorganic Electronic Spectroscopy**; 2nd ed.; Elsevier: New York, 1984; pg. 555.
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