Synthesis and catalytic activities of copper(I) complexes of Bis(diphenylphosphinomethyl)amino ligand and its Silica-supported form

Article abstract of DOI:10.1080/15533174.2010.509299

Cu(I) complexes of free ditertiary aminomethylphosphine ligand, N,N-bis(diphenylphosphinomethyl)aminopropyltriethox- ysilane (DIPAPTES) and its silica supported form (SiO2-DIPAPES), have been synthesized under nitrogen atmosphere using Schlenk method and characterized by atomic absorption, FT-IR, NMR (1H and 31P), and elemental analysis. Acetylacetonate (acac)- complexes of Cr(III) and Mn(III) complexes were prepared according to the literature. All the complexes were used as catalysts for the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-naphthoquinone (Vitamin K₃, menadione, 2MNQ) using hydrogen peroxide as a clean and cheap oxidant. All the complexes did not show good catalytic activity for the selective oxidation of 2-methyl naphthalene to 2-methyl-1,4-naphthoquinone. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/15533174.2010.509299

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Synthesis and Catalytic Activities of Copper(I)
Complexes of Bis(diphenylphosphinomethyl)amino
Ligand and its Silica-supported Form
a
b
c
Serhan Uruş , Mustafa Keleş & Osman Serindağ
a Department of Chemistry, Faculty of Science and Letters , Kilis 7 Aralık Üniversity ,
Kilis, Turkey
b Department of Chemistry, Faculty of Science and Letters , Osmaniye Korkut Ata
University , Osmaniye, Turkey
c Department of Chemistry, Faculty of Science and Letters , University of Çukurova ,
Adana, Turkey
Published online: 23 Oct 2010.
To cite this article: Serhan Uruş , Mustafa Keleş & Osman Serindağ (2010) Synthesis and Catalytic Activities of Copper(I)
Complexes of Bis(diphenylphosphinomethyl)amino Ligand and its Silica-supported Form, Synthesis and Reactivity in
Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40:9, 613-620
To link to this article: http://dx.doi.org/10.1080/15533174.2010.509299
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 40:613–620, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2010.509299
Synthesis and Catalytic Activities of Copper(I) Complexes of
Bis(diphenylphosphinomethyl)amino Ligand and its
Silica-supported Form
Serhan Urus¸,1 Mustafa Keles¸,2 and Osman Serindag˘3
1
¨
Department of Chemistry, Faculty of Science and Letters, Kilis 7 Aralık University, Kilis, Turkey
2Department of Chemistry, Faculty of Science and Letters, Osmaniye Korkut Ata University, Osmaniye,
Turkey
3Department of Chemistry, Faculty of Science and Letters, University of C¸ ukurova, Adana, Turkey
catalyst. Therefore, they can be sometimes used as catalytic
synthesis.[8−10]
Cu(I) complexes of free ditertiary aminomethylphosphine
ligand, N,N-bis(diphenylphosphinomethyl)aminopropyltriethox-
ysilane (DIPAPTES) and its silica supported form (SiO2-
DIPAPES), have been synthesized under nitrogen atmosphere
using Schlenk method and characterized by atomic absorption,
FT-IR, NMR (1H and 31P), and elemental analysis. Acetylacetonate
(acac)− complexes of Cr(III) and Mn(III) complexes were prepared
according to the literature. All the complexes were used as catalysts
for the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-
naphthoquinone (Vitamin K3, menadione, 2MNQ) using hydrogen
peroxide as a clean and cheap oxidant. All the complexes did not
show good catalytic activity for the selective oxidation of 2-methyl
naphthalene to 2-methyl-1,4-naphthoquinone.
Vitamins K are biologically active compounds that are kinds
of naphthoquinones, and are effective for blood coagulation.
Vitamin K3 is a synthetic member of vitamin K group. However,
vitamin K3 is more active than other vitamin K derivatives for
blood coagulation. The human body synthesizes vitamin K in
their intestine by microorganisms, but some animals have to get
vitamin K from feed.[2,3]
In the classical process, Vitamin K3 is produced via sto-
ichiometric oxidation of 2-methyl naphthalene with CrO3 in
sulphuric acid with the yield of 30–60%. After this reaction,
18,000 g. of chromium containing waste is obtained for the syn-
thesis of 1,000 g. menadione. It is too difficult to treat chromium
containing waste.[2,3] Alternatively, vitamin K3 can be cleanly
and modernly synthesized in high yield using hydrogen perox-
ide as clean oxidant in acetic acid via transportation of oxygen
in the presence of a catalyst.[2,3,11]
Keywords menadione, oxidation, phosphines, quinones, silica-
supported complexes, Vitamin K3
1. INTRODUCTION
Functionalized phosphine ligands and their transition metal
complexes have increasingly become important due to their im-
proved catalytic activity. Due to the fact that phosphines play an
efficient role on transportation of oxygen to substrate with a tran-
sition metal center, synthesis of novel aminomethylphosphine-
metal complexes, and investigation of their oxidative cat-
alytic properties are a part of modern production process
researches.[1−7]
2. EXPERIMENTAL
2.1. General
All synthesis reaction steps of the phosphine-complexes
were carried out under nitrogen atmosphere using Schlenk
method. 3ꢀ-Aminopropyltriethoxysilane (3ꢀ-APTES) was pur-
chased from Fluka. The phosphonium salt [PPh2(CH2OH)2]Cl,
which is a starting compound for the synthesis of phosphines,
and [Mn(acac)3], [Cr(acac)3] complexes were prepared as de-
scribed in the literature.[1−5,12,13] The liquid state NMR spectra
were recorded at 25◦C in DMSO-d6 and CDCl3 using a Varian
Mercury 200 MHz NMR spectrometer. 31P-NMR spectra were
recorded with complete proton decoupling and are reported in
ppm using 85% H3PO4 as external standard. Solid state NMR
spectra were measured using Bruker superconducting FT-NMR
spectrometer avance TN 300 MHz WB. FT-IR spectra were
Transition metal complexes of acetylacetonate (acac)− are
both a radical initiator and a hydroperoxide decomposition
Received 8 February 2010; accepted 12 July 2010.
The authors would like to thank to Oxyvit Kimya San. Tic. A. S¸.
for all their support. The authors also thank to C¸ ukurova University for
financial support (Project No: FEF2007D007).
Address correspondence to Serhan Urus¸, Department of Chemistry,
¨
Faculty of Science and Letters, Kilis 7 Aralık University, Kilis, Turkey.
E-mail: serhanurus@yahoo.co.uk
613

614
S. URUS¸ ET AL.
CH3
Further Oxidation
Methyl Group Oxidation
2−methyl naphthalene
O
O
CH2OH
CH3
H2O2
catalyst
HOAc
H2SO4
O
60-80 oC
CHO
O
O
O
O
O
CH3
CH3
CH3
CH3
O
COOH
2-methyl-1,4-Naphthoquinone
6-Methyl-1,4-Naphthoquinone
Other further oxidation and
coupling products
Carboxylic Acids
SCH. 1. Multiple pathways in the oxidation of 2-methyl naphthalene.[7]
obtained using KBr pellets with Perkin-Elmer RX1 FT-IR sys- stirred at room temperature for 4 h. Addition of diethylether
tem in the range 4000–450 cm−1. Elemental analyses were per- gave the yellow solid which was then filtered off and dried.
formed using LECO CHNS 932 instrument. During oxidation Yield 2.15 g (75%). C35H45NO3P2SiCuCl: calcd C 58.65, H
1
experiments, the reaction products were analyzed on a Varian 6.32, N 1.95%; anal. C 58.01, H 6.10, N 1.89 %. H-NMR
3800 GC (FID) with Silicone OV-17 packed column and char- (CDCl3, 25 ◦C, δ, ppm): 7.22-7.40 [m, 40H, 8Ph], 3.31 [m, 4H,
acterized by Perkin Elmer Clarus 500 GC-MS Electron Impact Si-CH2CH2], 2.40 [br, 8H, SiCH2CH2CH2N and P-CH2-N],
(70 eV) with an Elite 5-MS capillary column. Metal contents 1.32 [m, 4H, SiCH2CH2], 3.31 [m, 4H, ◦O-CH2CH3], 1.10 [m,
were determined by Perkin elmer analyst 400 atomic absorption. 6H, OCH2CH3]. 31P-NMR (CDCI3, 25 C, δ, ppm): 50,91 [s,
All chemicals and reagents were purchased from Merck, Riedel Cu-PPh2]. FT-IR (KBr, cm−1): 3070 (m, Ar-H); 2955 (m, R-H);
de Haen, Fluka, and Sigma, and all solvents were dried using 1634 (m, C C (Ph); 1455 (m, C-H); 1111 (m, C-N (ter-amine));
established procedures and immediately distilled nitrogen atmo- 802 (s, monosubstitue Ar-H).
sphere prior to use. Silica having particule size of 0.150–0.250
mm and density of 170–300 m2/g was used as solid support for
heterogeneous catalysts. [Mn(acac)3] (1) and [Cr(acac)3] (2)
complexes were prepared according to the literature.[12,13]
2.4. Preparation of [Cu(L2)2]Cl (4)
L2 (2.0 g) was added to a stirred solution of CuCl (0.396 g;
4 mmol) in ethyl alcohol (10 mL). The mixture was refluxed 6
h to give yellow solid which was then filtered off, rinsed with
CH2Cl2 and dried under vacuum. Yield 2.10 g. FT-IR (KBr,
cm−1) 3077 (m, Ar-H); 2955 (m, R-H), 1640 (w, C C (Ph)),
1161-1020 (m, C-N (ter-amine)), 803 (s, monosubstitute Ar-H).
Cu: 5.1% (AAS). 31P-NMR (solid, δ, ppm): 51.05 [s, Pt-PPh2].
Cu: 5.1% (AAS).
2.2. Preparation of L1 (DIPAPTES) and its silica supported
form L2 (SiO2-DIPAPES)
L1 (DIPAPTES) and its silica supported form L2 (SiO2-
DIPAPES) were synthesized using [PPh2(CH2OH)2]Cl and 3ꢀ-
aminopropyltriethoxysilane (3ꢀ-APTES) in a solution of NEt3
according to the literature.[2−7]
2.5. Catalytic Oxidation of 2-methyl Naphthalene with
Complexes 1, 2, 3 and 4
2.3. Preparation of [Cu(L1)2]Cl (3)
L1 (1.30 g, 2.1 mmol) was added to a stirred solution of CuCl
3.15 g 2-methyl naphthalene (0.0222 mol) and 0.1 g catalyst
(0.396 g, 4 mmol) in ethyl alcohol (10 mL). The mixture was for complex 1, 2 and 4, 0.5 g catalyst for complex 3 were used in

AMINOMETHYLPHOSPHINE AND ITS COMPLEXES
615
OCH2CH3
PPh2
NEt3
(CH2)3N
2[Ph2P(CH2OH)2]CI + (CH3CH2O)3Si(CH2)3NH2
H3CH2CO
Si
(L1)
ref lux
PPh2
OCH2CH3
CuCl
PPh2
Cu
Ph2P
Ph2P
OCH2CH3
(CH2)3N
OCH2CH3
H3CH2CO
Si
OCH2CH3
Cl
N(CH2)3
OCH2CH3
PPh2
OCH2CH3
(3)
OCH2CH3
O
Si
O
O
O
O
Toluene
Ref lux
O
O
Si OH
O
(CH3CH2O)3Si(CH2)3NH2
SiO
2
SiO
+
O
Si
O
O
Si
O
O
Si(CH2)3NH2
OCH2H2CH3
2
NEt3
H2O/EtOH
2(Ph2P(CH2OH)2)Cl
N2 atm.
H2
C
O
O
PPh2
PPh2
OCH2CH3
Si(CH2)3
SiO
2
(L2)
O
Si
O
O
Si
O
O
N
C
OCH2H2CH3
H2
CuCl
H2
OCH2H2CH3
(CH2)3Si
O
O
O
O
O
O
O
OCH2CH3
Si(CH2)3
H2C
PPh2
Ph2P
Ph2P
C
SiO
Cu
O
O
N
2
SiO
2
O
Si
O
O
Si
O
O
N
Cl
C
PPh2
OCH2CH3
CH2
OCH2H2CH3
H2
(4)
SCH. 2. Synthesis of Cu(I) complexes of free aminomethylphosphine ligand and its silica supported form.

616
S. URUS¸ ET AL.
O
O
H2O2
H+
H
O
O
O
H
Ph2
P
M
SiO2 (H2C)2N
P
Ph2
2H+
2MNQ
Ph2
O
Ph2
2MNO2H2
P
P
M
M
SiO2 (H2C)2N
SiO2 (H2C)2N
O
P
P
Ph2
Ph2
Metal-peroxo pre-complex
2MN
H+
Ph2
P
O2
Ph2
P
HCl
2MNOOH
M
M
SiO2 (H2C)2N
SiO2 (H2C)2N
2MN
P
P
Ph2
Ph2
SCH. 3. Possible mechanism of catalytic oxidation of 2MN.[2]
order to determine optimum oxidation time in the experiments. were characterized and verified by GC-MS. All experiments
Various oxidant and catalyst amount parameters were not in- were performed in triplicate.
vestigated for the oxidation of 2-methyl naphthalene using the
complexes 3 and 4.
RESULTS AND DISCUSSION
The catalytic reactions were carried out in a glass reactor
having a water circulator wrapping around it. Due to the dif- Catalyst Preparation
ficulties to keep the reaction temperature constant during the
oxidation reaction, the temperature was held around 60 5◦C.
2-methyl naphthalene and catalyst in glacial acetic acid and hy-
drogen peroxide containing sulfuric acid were pumped into the
reactor with a pump with the flow rate of 10 mL/min, respec-
tively. 2-methyl naphthalene, 2-methyl-1,4-naphthoquinone and
6-methyl-1,4-naphthoquinone (6MNQ, isomer) amounts were
calculated from external calibration curves prepared prior to
analysis. Catalytic reaction products, as shown in scheme 1,
L1 (DIPAPTES) and its silica supported form L2 (SiO2-
DIPAPES) were synthesized according to the reported
studies.[2−4] The novel [Cu(L1)2]Cl (3) and [Cu(L2)2]Cl (4)
complexes were synthesized using CuCl, as shown in Scheme 2.
Mn(III) and Cr(III) complexes of [CH3COCHCOCH3]− (acac−)
(L3) were prepared according to the literature.[11,12]
The colors of synthesized [Cu(L1)2]Cl (3) and [Cu(L2)2]Cl
(4) complexes were yellow, prepared [Mn(acac)3] (1) and
[Cr(acac)3] (2) complexes were maroon and dark,respectively.

AMINOMETHYLPHOSPHINE AND ITS COMPLEXES
617
TABLE 1
The multiplet peaks of P-CH2-N and NCH2CH2 protons of phos-
phine ligand L1 and its Cu(I) complex 3 was present around
2.4–2.5 ppm, which is in agreement with reported studies.[1−9]
31P-NMR data of the complexes
Ligands δP (ppm) Complexes δP (ppm) ꢀδ(ppm)a
1
The H-NMR spectra showed no remarkable differences be-
tween the free ligands and their metal complexes. The NCH2
resonances of the complexes are only slightly shifted to low
field compared to the free ligands, indicating that the N atom is
not coordinated, as also reported in the literature.[1,4−7,14,15]
31P-NMR spectra of the Cu-phosphine complexes showed
more shielded signals compared with the uncoordinated
aminomethylphosphine ligand. The coordination shift values
of the complexes 3 and 4 (ꢀ), as varied depending on the
metal centers and the chemical structures of the ligands showed
that the ligands were bound to metal centers via a P-P biden-
tate to give chelated complexes rather than M-N interaction
(Table 1).[14,15]
L1
L2
−28.2
−27.0
[Cu(L1)2]Cl
[Cu(L2)2]Cl
50.91
51.05
79.11
78.05
aCoordination shift values of the complexes ꢀδ = δP (complex)-δP
(free ligand).[9,10]
All the complexes except 4 are soluble in glacial acetic
acid.
The phosphonyl band and the P-aryl bands of the complexes
of 3 and 4 shifted to 1111 cm−1 and 3070 cm−1, 1161 cm−1 and
3077 cm−1, respectively. Assignment of these results showed
that P-aryl wave numbers of the metal complexes shifted to
higher values comparing with uncoordinated ligand if compared
to the free ligands in the literature.[1−7,14−16] The shifted spectra
of the ligand incorporated into the complexes indicated that the
ligand coordinated to metal ions.
Catalytic Activity
Phosphine-M complexes (Especially M: Pd, Pt) are known as
oxidative catalysts by peroxides. In the first step of the catalytic
The phosphine ligand and its silica-supported form and their process, 2MN is oxidized to 2-methyl-1-naphthol and then to
Cu(I) complexes were characterized using 1H-NMR, 31P-NMR, 2-methyl-1,4-naphthalenediol. Oxidation rate can be described
elemental analysis, and FT-IR. The proton signals of the phenyl as γ =k[cat][H2O2] formula. If the catalyst amount is a con-
ring in the free phosphine ligand and their metal complexes in stant, reaction rate is first-order with equation γ =k[H2O2].[2]
1H-NMR spectra were observed in the range of 7.3–6.9 ppm. According to the equation, hydrogen peroxide concentration
TABLE 2
Catalytic activity of the complexes
Yields (%)a
Catalyst
Amount of catalyst (g)
H2O2 (mL)
Time (h)
Conversion
2MNQ
6MNQ
0.05
0.10
0.20
0.1
10
10
10
5
1.0
1.0
1.0
1.0
1.0
0.5
1.5
1.0
1.0
1.0
1.0
1.0
0.5
1.5
0.5
1.0
1.5
0.5
1.0
1.5
50.84
68.25
69.44
43.28
75.24
54.00
80.41
51.25
70.08
71.23
45.80
77.85
55.75
81.01
48.01
67.24
79.91
49.22
67.09
79.91
10.50
12.38
13.56
10,44
14.26
11.65
17.24
10.10
14.18
14.85
11,40
15.80
12.10
19.75
9.20
0.98
2.55
2.75
0.58
2.67
0.82
2.89
1.25
2.12
2.78
0.65
2.85
0.91
2.76
1.04
1.11
2.30
0.62
0.69
1.41
1
15
0.10
0.25
0.50
1.00
0.50
10
10
10
10
5
2
15
0.50
0.50
10
10
3
4
14.55
20.71
8.56
11.04
16.54
0.50
10
aReaction conditions: 3.15 g (0.0222 mol) 2MN, 40 mL glacial acetic acid and 0.6 mL sulfuric acid (98 %), Temperature: 60◦C.

618
S. URUS¸ ET AL.
85
20
18
16
14
12
10
8
20
18
16
14
12
10
8
75
65
55
45
0,4
0,65
0,9
1,15
1,4
0,45
0,7
0,95
1,2
1,45
0,45
0,7
0,95
1,2
1,45
Reaction time (h)
Reaction Time (h)
Reaction Time (h)
1
2
3
4
1
2
3
4
1
2
3
4
FIG. 1. Influence of the reaction time on the catalytic oxidation of 2MN. Temperature: 60 ◦C, H2O2 = 10 mL, 2MN = 3,15 g (0.0222 mol).
directly affects the reaction. The first step is the rate determining The temperature was held around 60 5◦C. 2MN is oxidized
step because it is slow and needs to be controlled in order to by using Na2Cr2O7 / H2SO4 solution in a reactor having cool-
increase the 2MNQ selectivity.[2,3,18−23] The predicted catalytic ing water in order to keep the temperature 55–65◦C according
oxidation mechanism is shown in Scheme 3.[2]
to the classic industrial synthesis of 2MNQ. After the classi-
Homogeneous and heterogeneous catalysts experiments cal industrial synthesis of 2MNQ, 30–60% of 2MNQ yield is
were carried out using a similiar process. 2MN and catalyst obtained.[2,3,11,18−23]
dissolved in glacial acetic acid were pumped into the reactor,
The results of the blank reactions were indicated that 2MNQ
oxidation reaction was started when hydrogen peroxide and sul- yield, 3.7%, 5.3% and 15.9% with 30.5%, 40.2% and 68.7%
furic acid solution were pumped onto the substrate mixture. 2MN conversion analyzed on the 30. min., 60. min. and
80
70
60
50
40
30
20
10
80
70
60
50
40
30
20
10
0
0
Catalyst Amount (g)
Catalyst Amount (g)
0.05
0.1
0.2
0.25
0.5
1
51.25
10.1
1.25
70.08
14.18
2.12
71.23
14.85
2.78
50.84
10.5
0.98
68.25
12.38
2.55
69.44
13.56
2.75
2MN Conversion %
2MNQ Yield %
6MNQ Yield
2MN Conversion %
2MNQ Yield %
6MNQ Yield
FIG. 2. Influence of the amount of the complex 3 and 4 on the catalytic oxidation of 2MN. Temperature: 60◦C, H2O2 = 10 mL, 2MN = 3.15 g (0.0222 mol).

AMINOMETHYLPHOSPHINE AND ITS COMPLEXES
619
80
70
60
50
40
30
20
10
0
100
80
60
40
20
0
H2O2 (mL)
H2O2 (mL)
5.00
10
15
5.00
10
15
43.28
10.44
0.58
68.25
12.38
2.55
75.24
14.26
2.67
45.8
11.4
0.65
70.08
14.18
2.12
77.85
15.8
2.85
2MN Conversion %
2MNQ Yield %
2MN Conversion %
2MNQ Yield %
6MNQ Yield %
6MNQ Yield %
FIG. 3. Influence of the concentration of H2O2 on the catalytic oxidation of 2MN. Temperature: 60◦C, H2O2 = 10 mL, 2MN = 3.15 g (0.0222 mol), 0.1 g
complex 3 and 0.5 g complex 4.
90. min. Furthermore; different oxidant volumes (5, 10 and
15 mL) and different catalyst amounts (0.05, 0.1 and 0.2 g)
were tested in order to determine optimum reaction conditions,
respectively (Figures 1, 2, and 3).
Complexes [Mn(L3)3] (1), [Cr(L3)3] (2), [Cu(L1)2]Cl (3) and
[Cu(L2)2]Cl (4) did not show a good catalytic effect if compared
to our previous studies.[2,3] Due to the fact that further oxidation
products and undetermined products arised using complexes 1,
2, 3 and 4 with a medium conversion, the low 2MNQ yield
percentage were obtained.
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plexes of functionalized phosphines-II. Synthesis of hydroxymethyl-
and aminomethyldiphenylphosphine complexes of platinum. Crys-
tal structure of cis-[PtCl2(Ph2PCH2OH)2]. Polyhedron, 1993, 12(17),
2121–2124.
8. Gorkum, R.V., Bouwman, E., and Reedijk, J. Fast autoxidation of ethyl
linoleate catalyzed by [Mn(acac)3] and bipyridine: a possible drying catalyst
for alkyd paints. Inorg. Chem., 2004, 43 (8), 2456–2458.
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4. CONCLUSIONS
Bidentate tertiary phosphine complexes of Cu(II) with N, N-
bis(diphenylphosphinomethyl)aminopropyltriethoxysilane and
its silica supported form have been synthesized using Schlenk
method. Catalytic experiments were carried out in a glass reactor
having a cooling water circulating in its jacket. The coordina-
tion of the ligand to metal ions gave shielded chemical shifts
in NMR spectra in comparison with the free ligand. As a clean
and more efficient production of 2-methyl-1,4-naphthoquinone,
synthesized complexes were tested in glacial acetic acid con-
taining sulfuric acid. Complexes are not efficient, selective cat-
alysts compared to classical synthesis of 2-methyl naphthalene.
Because of obtaining the low yield after the results of the op-
timum reaction parameter tests, the silica-supported complex
[Cu(L2)2]Cl (4) were not applicable for the recycling experi-
ments and synthesis of industrial size.
10. Sumegi, L., and Norikov, Y.D. Studies on the decomposition of α-
phenylethyl-hydroperoxide catalyzed by metal-acetylacetonates. React.
Kinect. Catal. Lett., 1979, 11(4), 365–370.
11. Zalomaeva, O.A., Kholdeeva, O.A., and Sorokin, A.B. Preparation of
2-methyl-1,4-naphthoquinone (vitamin K3) by catalytic oxidation of 2-
methyl-1-naphthol in the presence of iron phthalocyanine supported cata-
lyst. C. R. Chimie, 2007, 10(7), 598–603.
12. Fernelius, W.C., and Blanch, J.E. Chromium (III) acetylacetonate: [tris(2,4-
pentanediono)chromium (III)]. Inorg. Syn. 1957, 5, 130.
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