Synthesis and spectral studies of some new bis(1,3-diketonato)palladium(II) complexes

Article abstract of DOI:10.1081/SIM-120020327

Bis(1,3-diketonato)palladium(II) complexes were synthesized by three routes. In route one, sodium hexachlorodipalladate in methanol was treated with the appropriately substituted diaryl-1,3-diketones using sodium carbonate, while in route two substituted

Full text of DOI:10.1081/SIM-120020327

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Synthesis and Reactivity in Inorganic and Metal-Organic
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Synthesis and Spectral Studies of Some New
bis(1,3‐Diketonato)palladium(II) Complexes
Vijai N. Pathak a , Chandra K. Oza a , Ragini Gupta b , Ranjana Tiwari a & Sarita Chaudhary a
a Department of Chemistry , University of Rajasthan , Jaipur, 302004, India
b Department of Chemistry , Malaviya Regional Engineering College , Jaipur, 302017, India
Published online: 15 Feb 2007.
To cite this article: Vijai N. Pathak , Chandra K. Oza , Ragini Gupta , Ranjana Tiwari & Sarita Chaudhary (2003) Synthesis and
Spectral Studies of Some New bis(1,3‐Diketonato)palladium(II) Complexes, Synthesis and Reactivity in Inorganic and Metal-
Organic Chemistry, 33:4, 607-624, DOI: 10.1081/SIM-120020327
To link to this article: http://dx.doi.org/10.1081/SIM-120020327
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 4, pp. 607–624, 2003
Synthesis and Spectral Studies of Some New
bis(1,3-Diketonato)palladium(II) Complexes
1
2
Vijai N. Pathak,1, Chandra K. Oza, Ragini Gupta,
*
Ranjana Tiwari,1 and Sarita Chaudhary1
1Department of Chemistry, University of Rajasthan, Jaipur, India
2Department of Chemistry, Malaviya Regional Engineering College,
Jaipur, India
ABSTRACT
Bis(1,3-diketonato)palladium(II) complexes were synthesized by three
routes. In route one, sodium hexachlorodipalladate in methanol was
treated with the appropriately substituted diaryl-1,3-diketones using
sodium carbonate, while in route two substituted diaryl-1,3-diketones
were treated with palladium chloride in acetone to afford the desired
bis(1,3-diketonato)palladium(II). In route three 1,3-bis(substituted aryl)-
prop-2-enones were treated with palladium chloride and sodium
hydrogen carbonate in THF to provide the oxygen insertion product,
bis(1,3-diketonato)palladium(II) complexes. All synthesized compounds
were characterized on the basis of spectral and analytical data.
*
Correspondence: Vijai N. Pathak, Department of Chemistry, University of
Rajasthan, Jaipur 302004, India; E-mail: pathakvn@yahoo.com.
607
DOI: 10.1081/SIM-120020327
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

608
Pathak et al.
INTRODUCTION
1,3-diketones constitute an important class of ligands in view of their
distinct structural properties and high synthetic utility. They exist in two
tautomeric forms[1] which have been extensively studied by NMR[2–6] and
Raman spectroscopy.[7,8] The metal complexes of these compounds have
considerable commercial interest. Metal 1,3-diketonates are used in the
production of laser devices,[9–13] as NMR shift reagents[14] and in analy-
tical chemistry.[15–17] The complexes of rhodium, europium and neo-
dymium are used as low-pressure hydroformylation catalysts,[18] UV sensi-
tive luminescent materials for inks and resins[19] and shielding agents for
plastics,[20] respectively. The mixture of organopolymer and transition metal
1,3-diketonates has produced image-recording materials.[21] Metal 1,3-
diketonates viz. palladium chelates[22–32] are used as homogeneous catalysts
in organic synthesis. Some reports have appeared on various modes of
bonding of 1,3-diketone with palladium.[33,34] The isolation of cis-bis-
(benzylacetonato)palladium(II) along with the isomeric unsymmetrical 1,3-
diketonates has been reported by Kawaguchi et al.[35]
In the present study we wish to report the synthesis of some bis(1,3-
diketonato)palladium(II) complexes from substituted diaryl-1,3-diketones
and 1,3-(substituted diaryl)prop-2-enones (chalcones). A perusal of the
literature revealed that there is only one reference[36] available concerning
the insertion reaction of oxygen to the prop-2-enone system. We have,
therefore, explored the possibilities of utilizing the general procedure for
oxygen insertion to various diphenylprop-2-enone systems to afford sub-
stituted diaryl-1,3-diketones. All the synthesized compounds have been
characterized by analytical and spectral data.
RESULTS AND DISCUSSION
Synthesis of bis(1,3-Diketonato)palladium(II) Complexes
The bis(1,3-diketonato)palladium(II) compounds (2a, b) were prepared
by reacting sodium hexachlorodipalladate (stock solution) with substituted
diaryl-1,3-diketones and sodium carbonate and compound (2c) was
prepared by the reaction of palladium chloride and substituted diaryl-1,3-
diketone in acetone while the bis(1,3-diketonato)palladium(II) complexes
(4a-f) were prepared by treating a mixture of palladium chloride with 1,3-
(substituted diaryl)prop-2-enones (3a-f) and sodium hydrogen carbonate in
THF (Figure 1).

bis(1,3-Diketonato)palladium(II) Complexes
609
Figure 1. Synthesis of bis(1,3-diketonato)palladium(II) complexes.
Compounds (2a-c) and (4a-f) and their physical characteristics and
analytical analyses are recorded in Tables 1 and 2, respectively.
IR Spectra of bis(1,3-Diketonato)palladium(II) Complexes
The various coordination modes of palladium viz.; Pd-O,O’-coordina-
tion, Pd-C-coordination and/or Pd-O,C-coordination with 1,3-diketones are
differentiated on the basis of IR spectral data.[37] The absence of absorption
bands around 1700 cm–1 rule out the possibilities of C- and O,C-
coordination modes. The appearance of > C=O absorption bands in the
region of 1620–1585 cm–1 is in harmony with keto-enolates, viz., Pd-O,O’-
coordination mode which corresponds to bis(1,3-diketonato)palladium(II)
chelates. The absorption bands between 1500–1480 cm–1 are attributed to
the > C=C < stretching mode coupled slightly with the C—H in-plane
bending mode. The absorption band in the region of 1415–1380 cm–1 is

610
Pathak et al.

bis(1,3-Diketonato)palladium(II) Complexes
611

612
Pathak et al.
assigned to the degenerate and asymmetric deformation vibrations of the
methyl group. The very strong absorption bands in the regions 1200–1120,
780–720 and 620–550 cm–1 are due to C—F, C—Cl and C—Br stretching
modes, respectively.
1H NMR Spectra of bis(1,3-Diketonato)palladium(II)
Complexes
The 1H NMR spectra of bis(1,3-diketonato)palladium(II) complexes
having halogen substituted phenyl group exhibited a characteristic,
beautiful, symmetrical AA’BB’ pattern[38] (Figures 2–4). Here the two
different kinds of protons are coupled together in a pattern that looks
superficially like an AB system, but actually has a number of extra lines, of
which the ‘inside lines’ are the most noticeable. The complexity in these
spectra comes from the fact that here the pairs of A nuclei (and B nuclei)
are not magnetically equivalent. Thus, a given A nucleus has very different
coupling constants to the two B nuclei. In case of fluorine substituted at the
para position of the phenyl ring (Figure 2) the AA’BB’ protons also couple
with fluorine to give a doublet of doublets.
1
In the H NMR spectra of bis[1-(4-bromophenyl)-1,3-butanedione]pal-
ladium(II) complex (2a) HA proton chemical shift signals are observed
downfield from d 7.736–7.826 ppm [coupling constant (J) in Hz, JHHAB
=
8.4, d] and for the HB protons the proton resonance signals are observed
from d 7.539–7.650 ppm [coupling constant (J) in Hz, JHHBA=8.7, d].
Compound (2b) again shows a double doublet due to coupling of HA pro-
tons wth HB and vice versa. HA proton resonance signal is observed
downfield from the region d 7.811–7.840 ppm [coupling constant (J) in Hz,
J
HHAB=8.7, d] and for the HB protons the proton resonance signals are
observed from d 7.413–7.385 ppm [coupling constant (J) in Hz, JHHBA
8.4, d]. In compound (2c) the proton chemical shift signal is observed from
d 7.838–7.927 ppm [coupling constant (J) in Hz, JHHAB=8.7, d; JHHAA’
=
=
3.1, d; JHF1,2’=9.0, d] while the proton chemical shift for the HB proton has
been noticed at a very unusual upfield value i.e. d 6.968–7.070 ppm
[coupling constant (J) in Hz, JHHBA=8.7, d; JHF1,3=6.6, d].
1
On the basis of H NMR, it has been concluded that the major mode of
coordination in our fluoro, bromo and chloro-substituted bis(1,3-diketana-
to)palladium(II) complexes is the ketoenolate (95.24 and 95%, respec-
tively). However, a very small percentage (4.76 and 5%, respectively) of
palladium is coordinated to the olefinic bond of the two chelate rings along
with two other ligands (chlorine). This is recognized by its chemical shift at
d 6.017 and 6.054 ppm which are upfield in contrast to O-chelated methine
protons which exhibit chemical shifts at d 6.14–6.15 ppm and 6.15 ppm,

bis(1,3-Diketonato)palladium(II) Complexes
613
Figure 2. 1H NMR spectrum of bis[1-(4-bromophenyl)-1,3-butanedione]-palla-
dium(II) complex (2a) at 300 MHz in CDCl3.
respectively. It is also interesting to note that the coordinated methine
proton chemical resonance is coupled with the ortho-phenyl proton by
o-coupling.[38] However, when fluorine is situated at the para position of
the phenyl ring it couples through long-range and space-coupling with the
ketoenolate methine proton resonance as well as methyl proton resonance at
2.15–2.23 and 2.21–2.24 ppm, respectively.

614
Pathak et al.
Figure 3. 1H NMR spectrum of bis[1-(4-chlorophenyl)-1,3-butanedione]-palla-
dium(II) complex (2b) at 300 MHz in CDCl3.
The 1H NMR spectra of the palladium chelates prepared from 1,3-
(substituted diaryl)prop-2-enones showed that the final product is a THF
adduct. The resonance signal due to the THF moiety is observed in the
region of d 1.2–1.4 ppm while the resonance signal due to the phenyl ring
is observed at d 6.5–7.5 ppm. The compounds having a methylenedioxy-
phenyl group (-O-CH2-O-) showed a resonance signal at d 5.4 ppm as a

bis(1,3-Diketonato)palladium(II) Complexes
615
Figure 4. 1H NMR spectrum of bis[1-(4-fluorophenyl)-1,3-butanedione]-palla-
dium(II) complex (2c) at 300 MHz in CDCl3.
sharp singlet and the compounds having a N,N-dimethylamino group
[N(CH3)2] showed a resonance signal at d 2.8–3.0 ppm. The peak due to
the central methine proton of the chelate ring is observed in the region of d
6.2–6.4 ppm.

616
Pathak et al.
Mass Spectra of bis(1,3-Diketonato)palladium(II)
Complexes
The mass spectra of compound (2b) (Table 1) under electron impact
exhibited molecular ion cluster at m/z 496, 498 and 500 indicating two
chlorine atoms along with their isotopic value 35Cl/37Cl (in the ratio of 9:
6:1). The base peak has been observed at an unusually low mass at m/z 44
corresponding to the protonated acyl moiety CH3–C=OH + , which is
Table 3. Major fragments in mass spectra of bis[1-(4-chlorophenyl)-1,3-
butanedione]palladium(II) complex (2b).
Fragment no. Composition of fragments
m/z
Relative intensity (%)
1.
[C20H16Cl2O4Pd] +
500 [37Cl]
498 [35/37Cl]
496 [35Cl]
417 [37Cl]a
413 [35Cl]
388 [37Cl]
384 [35Cl]
344 [37Cl]
342 [35Cl]
303 [37Cl]
301 [35Cl]
302 [37Cl]
300 [35Cl]
260 [37Cl]a
258 [35Cl]
218 [37Cl]
216 [35Cl]
198 [37Cl]
196 [35Cl]
183 [37Cl]
181 [35Cl]
141 [37Cl]
139 [35Cl]a
140 [37Cl]a
138 [35Cl]
113 [37Cl]a
111 [35Cl]
44
11.3
16.6
24.8
–
2.
3.
[C16H13Cl2O2Pd] +
[C14H8Cl2O2Pd] +
[C12H9ClO3Pd] +
[C10H8ClO2Pd] +
[C10H7ClO2Pd] +
[C8H5ClOPd] +
[C6H3ClPd] +
[C10H9ClO2] +
[C9H6ClO2] +
[C7H4ClO] +
9.6
5.4
10.4
19.1
32.1
20.1
11.2
6.8
4.
5.
6.
12.7
–
6.3
7.
8.
15.8
17
9.
11.4
61.4
23.4
64.7
48.7
–
10.
11.
12.
13.
14
[C7H3ClO] +
–
55.3
–
[C6H4Cl] +
35.3
100
[C2H4O] +
aThe intensity of these ions is less than 5%.

bis(1,3-Diketonato)palladium(II) Complexes
617
highly stabilized by resonance. Other important fragments and their relative
intensities are given in Table 3.
Compound (2c) (in Table 1) on 70eV impact does not exhibit the
molecular ion peak M + at m/z 464 indicating the instability of the
molecular ion in the ionization chamber. It easily fragments to cation
[C15H16FO4Pd] + . (m/z 385) by eliminating the fluorine-containing moiety
C5F (m/z 79). On the other hand, molecular ion in the ionization chamber
eliminates a ligand moiety to afford a cation radical with m/z 285
[C10H8FO2Pd] + . In compound (2c) the base peak is observed at m/z 123
which corresponds to FH4C6CO + cation which is highly stabilized by
resonance. A peak at m/z 44 is also observed (relative intensity 33.8%)
corresponding to fluoroacetylene cation radical (F–C=CH) +. which is
devoid of resonance, hence, is less stable. Other ions along with their
relative intensities are given in Table 4.
EXPERIMENTAL
IR spectra were recorded using a Perkin-Elmer model 557 and Nicholet
Magna model-750 spectrophotometer in KBr pellets at the Central Drug
Research Institute, Lucknow and the Department of Chemistry, University
1
of Rajasthan, Jaipur. H NMR spectra were recorded on a Jeol FX-90 Q
Table 4. Major fragments in mass spectra of bis[1-(4-fluorophenyl)-1,3-
butanedione]palladium(II) complex (2c).
Fragment no.
Composition of fragments
m/z
Relative intensity (%)
1.
2.
[C15H16FO4Pd] +
[C13H10FO4Pd] +
[C10H8FO2Pd] +
[C10H6FO2Pd] +
[C10H4FO2Pd] +
[C10H3FO2Pd] +
[C10H9FO2] +
[C10H9FO2] +
[C9H6FO2] +
[C9H6FO] +
385
355
285
283
281
280
180
179
165
149
123
95
2.6
2.6
3.
1.5
1.7
4.
5.
20.2
9.1
6.
7.
40.8
16.6
48.7
29.0
100
56.9
41.5
33.8
8.
9.
10.
11.
12.
13.
14.
[C7H4FO] +
[C6H4F] +
[C4H2F] +
69
44
[C2HF] +

618
Pathak et al.
spectrometer at 89.55 Hz in CDCl3 solution with TMS as an internal
standard. Mass spectra were recorded on Kratos-30 and 50 mass spectro-
meters at the Central Drug Research Institute, Lucknow. Melting points
were recorded in open capillaries and are uncorrected. All compounds are
homogeneous by TLC in various solvent systems.
Preparation of Ligands
Fluorobenzene and fluorochlorobenzene were prepared by the Balz-
Schieman reaction from the corresponding aromatic amines. Bromo-,
chloro- and fluoroacetophenones were prepared by the method of Buu-Hoi
et al.[39–41] The 1,3-diketones were prepared from the corresponding methyl
ketones by the general method reported earlier.[42]
Preparation of Stock Solution of Sodium
Hexachlorodipalladate in Methanol
A mixture of palladium chloride (5.6 mmol, 1 g) in methanol (50 mL)
and sodium chloride (5.6 mmol, 0.33 g in 25 mL of water) was refluxed for
2 h. Then the solution was filtered through cotton. Small traces of the
solution left in the original flask and on the cotton plug were washed with
methanol (10 mL). This 60 mL brownish black stock solution was assumed
to be 5.6 mmolar in palladium(II).
Preparation of bis(1,3-Diketonato)palladium(II) (2a-c)
from Substituted Aryl-1,3-diketones
First Procedure. The desired bis(1,3-diketonato)palladium(II) com-
pounds (2a-b) were prepared by the method of White.[43] A mixture of the
stock solution (1.8 mmol of Na2Pd2Cl6, 20 mL), the appropriately substi-
tuted diaryl-1,3-diketone (3.6 mmol) and sodium carbonate (3.6 mmol,
0.3816 g) was stirred for 8 h. The precipitate was filtered, dried and dis-
solved in chloroform (10 mL). This solution was chromatographed over
silica gel using carbon tetrachloride as eluant. Evaporation of the eluate
afforded the desired bis(1,3-diketanato)palladium(II) compounds (2a-b),
Table 1, which were recrystallized from hexane.
Second Procedure. To a hot solution of palladium chloride (0.5 mmol,
0.08 g) in acetone (20 mL) was added a solution of 1-(4-fluorophenyl)-1,3-
butanedione (0.1 mmol, 0.18 g) in ethanol (20 mL)[44] and then was stirred
for 30 min. The resultant mixture was concentrated and the solid thus
obtained was filtered, dried and recrystallized from hexane (compound (2c),
Table 1).

bis(1,3-Diketonato)palladium(II) Complexes
619

620
Pathak et al.
Preparation of 1,3-(Substituted Diaryl)prop-2-enones
(Chalcones) (3a-f)
The title compounds [(3a-f) Table 5] were prepared by following the
method of Joshi et al.[44] A mixture of appropriately substituted ace-
tophenone (0.29 mol) and aromatic aldehyde (0.29 mol) was dissolved in
the minimum amount of ethanol and then stirred at room temperature for 15
min. Sufficient 2 M aqueous NaOH was then added to render the solution
alkaline and the whole reaction mixture was further stirred for nearly 0.5 h.
It was neutralized with 2M HCl, diluted with water and left to stand
overnight. The precipitated chalcone was filtered, washed with water
(2 Â 50 mL) and recrystallised from ethanol as yellow needles. All the
compounds were homogeneous on TLC in various solvent systems.
Preparation of bis(1,3-Diketonato)palladium(II) (4a-f)
from 1,3-(Substituted Diaryl)-prop-2-enones
The title compounds [(4a-f) Table 4] were prepared by stirring a
mixture of palladium chloride (1 mmol, 0.1774 g), 1,3-(substituted
diaryl)prop-2-enones (0.666 mmol) and sodium hydrogen carbonate (1
mmol, 0.084 g) in peroxide-free THF (25 mL) for 36 h at room temperature
and then this mixture was refluxed for 40 h.[36] The progress of the reac-
tion was monitored by TLC and when the reaction was complete the
solution was filtered. The filtrate was concentrated to half its volume to
afford the desired bis(1,3-diketanato)palladium(II) which was recrystallized
from hexane.
ACKNOWLEDGMENTS
The authors are thankful to the Council of Scientific and Industrial
Research, New Delhi, for financial help and Dr. V.J. Ram, Scientist-E-II,
Medicinal Chemistry Division, Central Drug Research Institute, Lucknow,
for valuable suggestions.
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Received: February 15, 2002
Accepted: December 18, 2002
Referee I: J. D. Wardeska
Referee II: D. T. Haworth