IV.

SYNTHESIS OF AZOSALENS AND ORTHONICKELATION

IV.1. Background

Synthesis of N-[2-(arylazo)phenyl]salicylidenearrine, (H2Lsal), has been

described in the year 2008 by Chattopadhyay et. al. Before that there
was no report on preparation of this ligand. The C-H bondcleavage via
M-C bond formation were identified as one of the precondition of metal
assisted C-H activation.1-3 Several bi- and tri- dentate azo ligands have
been utilized for the purpose of preparation of stable compounds with M-
C(aryl) bonds.1-3 In this regard, it is worthwhile to mention that during
orthometallation, initial coordination of the hetero dorror atoms within
such ligands influence the facile metallation at the ortho carbon of
pendant aryl rings.l-3 Although, the orthometallation in bi- and tri- dentate
azo and imine ligands have been demonstrated amply in the cases of
heavier cougeners of Gr. l0 metals, i.e.
Pd(ll) and Pt(ll),1-3 but it is scarce for Ni(ll).4

lV. 2. Synthesis

The reaction was performed by refluxing an equivalent mixture of 2-

(arylazo) aniline
(HL-NH2) and a slight excess of salicylaldehyde in diethyl ether. The
ligands H2Lsal, I\/.1, were synthesized successfully by refluxing
salicylaldehyde with 2-(phenyl azo) aniline (HL1-NH2), 2-(p-tolyl azo)
aniline (HL2-NH2) and 2-(p-chloro phenyl
azo) aniline (HL3-NH2) respectively in diethyl ether medium. The
balanced equation has been
given in Eq 1. The desired pure products were obtained as orange solid
upon evaporation of
the solvents.

Reaction of H2Lsal with nickel acetate tetrahydrate, Ni(CH3COO)2.4H2O in

refluxing methanol precipitated the green orthonickelated complex
(Lsal)Ni,IV.2, which was collected by filtration. The reaction is shown in
Eq 2. A little more crop of product was isolated upon concentrating the
filtrate.
All the newly synthesized orthonickelated complexes are soluble in
common organic solvents giving a green solution. Three complexes
were prepared with H2L1sal, H2L2saland H2L3sal. The solution of (Lsal)Ni is
non conducting indicating the formation of molecular complex as
formulated.

It was observed that in the case of (L3sal)Ni the reaction time

was longer than (L2sal)Ni and (L1sal)Ni for orthometallation. The electron
withdrawing nature of Cl (-I effect) reduces the electron density at ortho
carbon of pendent aryl ring attenuating the ease of cyclomatallation.

IV. Characterisation

The C,H,N analysis were performed for ligands and their metal
complexes. On the basis of the analytical data the composition of the
complexes could be realized. The analytical data are collected in Table 1

Uv-vis-
Ligands H2Lsal displayed cherecteristic UV-vis spectra in
dichloromethane solution. A broad absorption at ~ 320nm were assigned
for n→n* transition of azo and aldimine functions.5 The higher energy
absorption at ~230nm were assigned for π→π* transition. The UV –vis
spectra H2L1sal, has been shown in figure IV.1. The UV-vis spectral data
are collected in Table 2

The UV-vis spectra of green solutions of (Lsal)Ni in CH2Cl2 feature of a

relatively weak absorption band near 630nm for d-d transition. 6 Four
absorption bands were observed in 315 to 460 nm range for MLCT
transitions (N=N and C=N).5a The UV-vis spectra of (L1sal)Ni has been
shown in Figure IV.2.

IR

The IR spectra of all the H2Lsal ligands displayed sharp single band
appeared near 1615cm-1 characteristic of ⱱC=N5. The IR band near 1452
cm-1 is assigned to ⱱN=N by comparing the same for other azo ligands2.
However, the ⱱOH for phenolic OH of salycylidine fragment is absent
consistent with the hydrogen bonded form of H2Lsal as shown in Eq. 2.
The IR spectral data are collected in table 2. The IR spectrum of H2L1sal
is given in figures IV.3.
In case of (Lsal)Ni the IR band near 1450cm-1 is assigned to ⱱN=N by
comparing the same for other azo ligands and considering the ex tent of
red shift upon coordination.7 The ⱱC=N and ⱱN=N of H2Lsal ligands
(~1615cm-1 and ~1452 cm-1 respectively )are shifted to lower wave
number (~1605 cm-1 and ~1430cm-1 respectively) for all the (Lsal)Ni
complexes, as expected for coordination of aldimine (N=CH) and azo
(N=N) nitrogen. The IR spectral data are collected in table 2. The IR
spectrum of (L1sal)Ni, is given in figure IV.4.
NMR

The aldimine proton (-N=CH-) resonances for H2Lsal appeared in the

range ~8.61-8.65 ẟ as a sharp singlet. 4b.8 A singlet resonance at 13.59 ẟ
assigned for phenolic proton4b of H2L1sal. Thirteen aromatic protons of
H2L1sal appeared within the aromatic region (ẟ 6.9- ẟ-8.0) in the sets of
three doublets at ẟ 7.06, ẟ 7.46 and ẟ 7.78; two triplets at ẟ 6.91, ẟ 7.33;
three multiplets within the ranges ẟ 7.36- ẟ 7.39, ẟ7.48 - ẟ 7.52 and ẟ
7.92- ẟ7.95. A total of twelve aromatic protons of H2L2sal appeared as
two doublets at ẟ 7.31 and ẟ 7.85 each of two equivalent protons.
Amongst the expected other four doublets two are observed at ẟ7.06
and ẟ7.78 while the other two appeared with in the multiplet in the range
of ẟ7.38- ẟ7.40 overlapped by one of the four triplets. Other three triplets
appear at ẟ6.93, ẟ7.36 and ẟ7.51. The aromatic protons of H2L3sal ligand
exhibited similar 1H NMR spectral pattern as that of H2L2sal with
differences in chemical shift values. 1H NMR spectral data are collected
in Table 3. The 1H NMR spectrum of H2L1sal, is given in figure IV.5.

The 1H NMR spectra exhibited that the aldimino proton (N=CH)

of (Lsal)Ni complexes shifted marginally upfield (ẟ 8.43- ẟ8.57) relative to
the ligands (~ẟ 8.62). The –OH signal of free ligands (~ẟ13.60) is absent
Nickel complexes indicating deprotonation of phenolic group and their
coordination to the metal as phenoxide. The 1H NMR of (L1sal)Ni twelve
aromatic protons appeared within ẟ6.57 to ẟ7.67 as one triplet at ẟ6.57,
three doublet at ẟ6.97, ẟ7.56 and ẟ7.67 and four multiplet at ẟ7.08-7.12,
ẟ7.14-7.18, ẟ 7.39-7.42 and ẟ 7.23 -7.27. In the 1H NMR (L2sal)Ni the
eleven aromatic protons appears within ẟ6.57 - ẟ7.65 and the 1H NMR
(L3sal)Ni the eleven aromatic protons appears within ẟ6.55 - ẟ7.62. The
spectral characteristics and integration are consistent with the structural
formula shown in Data are collected in Table3. The 1H NMR spectrum of
(L1sal)Ni, is given in figure IV.6.

IV.5. Experimental

Materials and physical measurements:

The solvents used in the reactions were of reagent grade obtained from
E.Merck, Kolkata, India and were purified and dried by reported
procedures. Ni(OAc)2.4H2O was perchased from Loba.

Electronic spectra were recorded on a Shimadzu UV-1800 PC

spectrophotometer. IR spectra were taken on a Parkin-Elmer L120-00A
FT IR spectrophotometer (4000-225 cm-1) in KBr pellets. C, H, N
analyses were performed on a Parkin-Elmer 240C elemental analyser.
NMR spectra were drawn on a Brucker Avance RPX 400 MHz
spectrometer in CDCl3 using TMS as the internal standard.

Synthesis of H2Lsal: The ligands H2L1sal, H2L3sal were synthesized

following the same general of which details procedure for H2L1sal are
given below.

Synthesis of H2L1sal : 2-(phenylazo) aniline (L1) (100mg , .50mmol) was

dissolved in diethylether (40ml), and to it salicylaldehyde (67mg,
0.55mmol) was added. The mixture was then heated to reflux for 8h and
then solvent was eavpourated in vacuo for two hour to obtained the solid
product eliminating the excess of salicylaldehyde. It was further kept in a
vacuum desiccator for 24h before the use and characterization.
m.p.960C. Isolated yield :95%.

Synthesis of H2L2sal: 2-(p-Tolylazo)aniline(H2L2) (100mg, 0.47mmol) was

dissolved in diethylether (40mL), and to it salicylaldehyde (61mg,
0.50mmol) was added. The mixture was then heated to reflux for 8h and
then solvent was evaporated in vaccuo for 2h to obtain the solid product
eliminating the excess of salicylaldehyde. It was further kept in a vacuum
desiccator for 24h before use and characterisation. m.p.840C. Isolated
yield;95%
Synthesis of H2L3sal: 2-(p-chlorophenylazo)aniline(H2L3)(100mg,
0.41mmol) was dissolved in diethylether (40mL), and to it
salicylaldehyde (61mg, 0.50mmol) was added. The mixture was then
heated to reflux for 8h and then solvent was evaporated in vaccuo for 2h
to obtained the solid product eliminating the excess of salicylaldehyde. It
was further kept in a vacuum desiccator for 24h before use and
characterisation. m.p.920C . isolated yield :95%

Synthesis of complexes:
Complexes of Ni(II), (Lsal)Ni: All the three complexes were prepared by
similar procedure. The detailed for the preparation of (L1sal)Ni, is given
below
Preparation of (L1sal)Ni: H2L1sal(120mg, 0.40mmol) was dissolved in
methanol (40mL), and to it Ni(OAc)2.4H2O (100mg, 0.40mmol) was
added. The mixture was then heated to reflux for 12h to obtained green
precipitate of (L1sal)Ni. The solid product was then filtered and washed
with water and a little ethanol. The volume of the filtrate was reduced to
~20mL and kept in a beaker covering with a watch glass. After 12h a
little more crop of product was collected by filtration. All the product were
taken together and recrystallized from dichloromethane-petroleum ether
to obtain pure (L1sal)Ni. Yield: 70%

Preparation of (L2sal)Ni: This complex was prepared following a similar

procedure as described for (L1sal)Ni using ligand (L2sal)Ni in place of
(L1sal)Ni. Yield: 60%

Preparation of (L3sal)Ni: This complex was prepared following a similar

procedure as described for (L1sal)Ni using complex (L3sal)Ni in place of
(L1sal)Ni. Yield: 62%.

VI. SYNTHESIS OF NEW N-BENZYLATED PHENOLATO LIGAND

AND REACTION WITH Cu(II)
V.1 Background

Synthesis of new phenolato ligand 1 N-(benzyl)-2-arylazo aniline has

been reported. Corresponding Nickel complexes were prepared to justify
the oxygen insertion into the Cu-C bond.

VI.2.Synthesis

Benzylation of HOL1-NH2
Several reaction processes have been tried for benzylation of aromatic
amines. Among these, the reaction of amine with benzyl bromide in
presence of bases like K2CO3 with catalytic amount of KI in ethanol or
dry acetonitrile, NEt3 with catalytic amount of KI in dry acetonitrile and
also reduction of Schiff’s base of amine and benzaldehyde by sodium
borohydride. But all the processes did not work for our purpose of N-
benzylation of HOL-NH2. In case of K2CO3 both N and O-benzylated
product was obtained, in case of NEt3 as base N-benzylated as well as
O-benzylated product was obtained as shown in Eq. 1-3.
After several attempts only N-benzylated product was obtained upon the
reaction of HOL-NH2 and benzylbromide in presence of pyridine base
and catalytic amount of KI in dry acetonitrile medium as shown in Eq.4.

Complexation with (HOL-NHCH2Ph)

Reaction of (HL-NHCH2Ph) with Cu(NO3)2.2H2O in methanol in presence

of slight temperature afforded dark brown coloured complexes of
composition (OL-NHCH2Ph)Cu(NO3)(H2O) as shown in Eq 5.
VI.4. Characterisation

The C,H,N analyses were performed for ligands and their metal
complexes. On the basis of analytical data the composition of the
complexes could be realised. The analytical data are collected in Table
1.

UV-vis
The ligands (HOL-NHCH2Ph) and corresponding copper complexes (L-
NHCH2Ph)Cu(NO3)(H2O) has been shown in figure VI.1. It is interesting
to observe that the UV-vis spectra of all the dark brown copper
complexes are similar with a low energy split band in the range of 519-
510nm and a structured band within the value of 410nm to 360nm. The
spectral data for all the ligands and complexes are collected in Table 2.
IR
The ligands (HOL-NHCH2Ph) exhibit characteristic IR spectra . The ⱱN-H
appeared as a single stretch in the range of 3031-3059 cm-1. The ⱱN=N
appeared (1565-1569cm-1) of all the ligands. The IR data for all the
ligands have been collected in Table 2. Representative IR spectrum of
(HOL1-NHCH2Ph) ligand have been shown in figure VI.2.
In case of complexes (OL-
NHCH2Ph)Cu(NO3)(H2O) ⱱN-H appeared with in the range 3283cm-1 to
3071 cm-1 and ⱱN=N shifted to lower frequency (1394cm-1 to 1383 cm-1) in
the complexes than that of ligands, consistent with coordination of azo
nitrogen. Representative IR spectra of (OL1-NHCH2Ph)Cu(NO3)(H2O)
complex have been shown in figure VI.3 and IR data are collected in
Table 2

NMR
The 1H NMR spectra of the (HOL-NHCH2Ph) ligands are consistent
with the composition and structure. In case of (HOL1-NHCH2Ph) the
phenolic OH appears as singlet at ẟ12.86 and NH2 proton at ẟ 6.19
disappeared. The CH2 protons appeared at ~ ẟ 4.48 and NH proton was
not appeared. All other aromatic protons appeared within ẟ 7.70-6.67 as
three doublets at ẟ 7.69 for one equivalent proton, ẟ 7.43 for one
equivalent proton and at ẟ 7.32 for three equivalent protons four
multiplets within ẟ 7.29-7.23, ẟ 7.21-7.11 for one equivalent proton and ẟ
6.92-6.86 and ẟ 6.77-6.67 for two equivalent proton respectively. In case
of (HOL2-NHCH2Ph) the phenolic OH appears as singlet at ~ ẟ 12.82
and NH2 proton at ẟ 6.19 disappear. The CH2 protons appeared at ~ ẟ
4.47 and NH proton was not appeared. All other aromatic protons
appeared within ẟ 7.60-6.70 as three doublets at ẟ7.60, ẟ7.24 and ẟ6.71
for one equivalent protons, one multiplet within ẟ7.33-7.25 for four
equivalent protons and two triplet at ẟ7.17 and ẟ6.83 for three and two
equivalent proton respectively. CH2 protons appeared at ẟ 2.31 as
singlet for three equivalent protons. In case of (HOL3-NHCH2Ph) the
phenolic OH appears as singlet at ~ ẟ13.11 and NH2 proton at ẟ 6.19
disappeared. The CH2 protons appeared at ~ ẟ4.46 and NH proton was
not appeared. All other aromatic protons appeared with in ẟ 7.79 to 6.70
as one doublet at ẟ 7.79 one equivalent proton, one triplet at ẟ 7.59 for
two equivalent protons and three multiplet within ẟ 7.43-7.27 for four
equivalents protons, ẟ 7.24-7.04 for three equivalent protons and ẟ 6.76-
6.70 for two equivalent protons respectively.
This spectral nature is consistent with the structural formula.
The original 1H NMR spectra of (HOL1-NHCH2Ph) is given in the figure
VI.5.
The 1H NMR spectra of (OL1-NHCH2Ph)Cu(NO3)(H2O) complex is
very complicated but one thing is clear that phenolic OH signal is absent
which indicates the coordination of phenolic OH. The 1H NMR of (OL1-
NHCH2Ph)Cu(NO3)(H2O) is given in figure VI.6.

VI.5 Experimental
Materials and physical measurements:

The solvent used in the reactions were of reagent grade obtained from
E.Merck, Kolkata, India and were purified and dried by reported
procedures. Pyridine, benzylbromide, potassium iodide were purchased
from E.Merck, Kolkata, India.
Electronic spectra were recorded on a Shimadzu UV-1800 PC
spectrophotometer. IR spectra were taken on a Parkin-Elmer L120-00A
FT IR spectrophotometer (4000-225 cm-1) in KBr pellets. C, H, N
analyses were performed on a Parkin-Elmer 240C elemental analyser.
NMR spectra were drawn on a Brucker Avance RPX 400 MHz
spectrometer in CDCl3 using TMS as the internal standard.

Synthesis of HOL-NHCH2Ph
All three ligands HOL1-NHCH2Ph, HOL2-NHCH2Ph and HOL3-NHCH2Ph
have been prepared by same procedure. The detailed procedure for the
preparation of HOL1-NHCH2Ph through various paths have been
illustrated.
HOL1-NHCH2Ph: A solution of benzylchloride (59.11mg,
0.467mmol) in ethanol was slowly added to the solution of HOL1-NH2
(100mg, 0.467mmol) in ethanol followed by addition of small amount of
base K2CO3 and catalytic amount of KI. The mixture was then heated to
reflux for 12hrs. The solvent was then evaporated to obtained orange
yellow solid mass. The product was then dissolved in dichloromethane
and was purified by preparative TLC using pet ether:benzene (90:10) as
eluent. Upon evaporation of solvent the crude complex was obtained.
The benzylation was obtained at both O- and N- position. Isolated
yield:60%
HOL1-NHCH2Ph: A solution of benzyl chloride(59.11mg,
0.467mmol) in dry acetonitrile as solvent was slowly added to the
solution of HOL1-NH2 (100mg, 0.467mmol) in dry acetonitrile followed by
addition of small amount of base K2CO3 and catalytic amount of KI. The
mixture was then heated to reflux for 12hrs. The solvent was then
evaporated for 0.5hrs to obtained orange yellow solid mass after
removal of excess solvent present. The product was then dissolved in
dichloromethane and was purified by preparative TLC using pet ether :
benzene (90:10) as eluent. Upon evaporation of solvent the crude
complex was obtained. A mixture of two benzylated product was
obtained: O- benzylated product and both N-benzylated and O-
benzylated product. Isolated yield:60%
HOL1-NHCH2Ph: A solution of benzyl chloride(59.11mg,
0.467mmol) in dry acetonitrile as solvent was slowly added to the
solution of HOL1-NH2 (100mg, 0.467mmol) in dry acetonitrile followed by
addition of small amount of base NEt3 and catalytic amount of KI. The
mixture was then heated to reflux for 12hrs. The solvent was then
evaporated to obtained orange yellow solid mass after removal of
excess solvent present. The product was then dissolved in
dichloromethane and was purified by preparative TLC using pet ether :
benzene (90:10) as eluent. Upon evaporation of solvent the crude
complex was obtained. A mixture of two benzylated product was
obtained: O- benzylated product and both N-benzylated and O-
benzylated product. Isolated yield:65%
HOL1-NHCH2Ph: To a solution of HOL1-NH2 (50.0mg, 0.234mmol) in dry
ethanol, slight excess of benzaldehyde (55.0mg, 0.240mmol) was
added. The mixture of heated to reflux for 7hrs in presence of dry
MgSO4. The solution was filtered and evaporation of solvent orange
solid mass was obtained. Isolated yield:95%. Further this orange solid
mass (50mg, 0.mmol) was dissolved in dry ethanol and NaBH4 (1.0g)
was added. The mixture was stirred for 1 hr. Upon evaporation of the
solvent red solid product was obtained. After spectral analysis it was
observed that this was not desired product.
HOL1-NHCH2Ph: A solution of benzyl bromide (80.2mg, 0.469mmol) in
dry acetonitrile as solvent was slowly added to the solution of HOL1-NH2
(100mg, 0.469mmol) in dry acetonitrile followed by addition of 111.3mg
pyridine (2-3drops) as base and catalytic amount of KI. The mixture was
then heated to reflux for 12hrs. The solvent was then evaporated for
0.5hrs to obtained orange yellow solid mass after removal of excess
solvent present. The product was then dissolved in dichloromethane and
was purified by preparative TLC using pet ether: benzene (90:10) as
eluent. Upon evaporation of solvent the crude complex was obtained
and isolated. The procedure afforded selective benzylation at N-position.
Isolated yield:40%
HOL2-NHCH2Ph: The HOL2-NHCH2Ph ligand was prepared following the
similar method as described in the case of HL1-NHCH2Ph, but using
HOL2-NH2 in place of HOL1-NH2. The eluent was petroleum ether. Upon
evaporation of solvent the orange-red solid of pure HOL2-NH2 was
obtained. Isolated yield:45%
HOL3-NHCH2Ph: HOL3-NHCH2Ph ligand was prepared following the
similar method as described in the case of HL1-NHCH2Ph but using
HOL3-NH2 in place of HOL1-NH2. The eluent was petroleum ether. Upon
evaporation of solvent the orange-red solid of pure HOL3-NH2 was
obtained. Isolated yield: 40%
Synthesis of (OL-NHCH2Ph)Cu(NO3)(H2O):
The complex of (OL-NHCH2Ph)Cu(NO3)(H2O) has been prepared by
following procedure. The detailed procedure has been illustrated
(OL2-NHCH2Ph)Cu(NO3)(H2O): A solution of HOL2-NHCH2Ph (0.150g,
0.52mmol) in methanol (10mL) was added drop wise to stirred solution
of Cu(NO3)2.2H2O(***************) in methanol. Immediately colour of the
solution began to change from orange yellow to violet-pink. The stirring
was continued for 18hrs with mild heat. The methanol was dried and a
brown coloured mass was separated out. The product was then
dissolved in dichloromethane and was then purified by preparative TLC
using benzene : acetonitrile (95:5) as eluent. Upon evaporation of
solvent the crude complex was obtained. Isolated yield:40%