Synthesis and multinuclear NMR study of a new benzoyl methylene triparatolylphosphorine ylide and its reactions with mercury (II) halides

Article abstract of DOI:10.1080/104265091001290

The reaction of bromoacetophenone with triparatolylphosphine in chloroform solution gives {Hooch (p-tolyl)₃}(I); then reaction of this new ylide with mercury (II) halides (HgCl₂, HgBr₂, Hgl₂) in equimolar ratio

Full text of DOI:10.1080/104265091001290

Phosphorus, Sulfur, and Silicon, 181:447–452, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265091001290
Synthesis and Multinuclear NMR Study of a New Benzoyl
Methylene Triparatolylphosphorine Ylide and its
Reactions with Mercury (II) Halides
Seyyed Javad Sabounchei
Sepideh Samiee
Kazem Karami
Chemistry Department, Bu-Ali-Sina University, Hamadan, Iran
The reaction of bromoacetophenone with triparatolylphosphine in chloroform so-
lution gives {Hooch (p-tolyl)3}(I); then reaction of this new ylide with mercury
(II) halides (HgCl2, HgBr2, Hgl2) in equimolar ratio leads to pure compounds
of [{(p-tolyl)3PCHCOC6H5}HgCl2]2 (II). [{(p-tolyl)3PCHCOC6H5}. HgBr2]2 (III),
and [{(p-tolyl)3PCHCOC6H5}Hgl2]2 (IV) complexes. The IR 1H13C, and 31P NMR
together, with microanalysis data of the products, were obtained.
Keywords Mercury (II) halides; phosphorus ylide; triparatolylphosphine
INTRODUCTION
Among the phosphorus ylides of general stoichiometry R3PCRꢀ(R, Rꢀ =
alkyl, alkoxy, etc.) the α-keto-stabilized ylides Ph3PCHCOR have shown
useful application in organometallic chemistry (due to their ambiden-
tate character as ligands1) and as reactants or valuable key intermedi-
ates in metal-mediated organic synthesis.1,2 This ambidentate charac-
ter facilitates the preparation of stable metal complexes in which the
ylide could be O-(A1, A2, Scheme 1)3−7 or C-coordinated (B).8−10 With
both, modes rationalized in terms of the resonance forms a–c together
with the isomeric formed. However, while a large number of compounds
containing C-coordinated ylides are known, very few examples of O-
bonded ones have been reported:3−7
The phosphorus ylide complexes have been well investigated. They
are versatile ligands for catalysts in a very small number of catalytic
Received December 2, 2004; accepted March 1, 2005.
We are grateful to the University of Bu-Ali-Sina for a grant and Mr. Zebarjadian for
recording the NMR spectra.
Address correspondence to S. J. Sabounchei, Department of Chemistry, Bu-Ali-Sina
University, Hamadan 65174, Iran. E-mail: jsabounchei@yahoo.co.uk
447

448
S. J. Sabounchei et al.
SCHEME 1
reactions, such as, for example, the hydrogenation of olefins and the
cyclotrimerization and polymerization of acetylenes, but the most im-
portant application is in the industrially used SHOP process.11 Thus
complexes (I), (II), and (III) obtained from the reaction of the new α-
carbonyl-stablized ylide (I) with HgX2 (X = Cl, Br and I).
EXPERIMENTAL
Methanol (MeOH) and diethyl ether (Et2O) were distilled over Mg or Na
and CH2Cl2 over CaH2 just before use. All other solvents were reagent
grade and used without further purifications. Melting points were mea-
sured with a SMPI apparatus. Solid-state FT-IR spectra in the region
of 400–4000 cm−1 using KBr pellets were obtained on a (Perkin Elmer)
1
spectrophotometer. H and 31P spectra were obtained using a 90 MHz
instrument at regional sophisticated instrumentation at Bu-Ali Sina
University, and 13C NMR spectra were measured with a BRUKER DRX-
500 spectrometer. Elemental analyses were carried out at the Research
Institute of Petroleum Industry.
Synthesis
Synthsise of {(p-tolyl)3PCHCOC6H5}
Tri-p-tolylphosphen 0.152 gr(0.5 mmol) was added in a chloroform
(25 mL) to a solution of bromoacetophenpon 0.099 gr (0.5 mmol) in
chloroform (20 mL) and the mixture was stirred for 4 h. The solution
was filtered off and the precipitate was washed with diethylether and
collected and dried. Then the reaction mixture was made basic by using
NaOH (5%), and a white-yellow precipitate was obtained. Yield: 0.152 gr

New Benzoyl Methylene Triparatolylphosphorine Ylide
449
(70%). m.p. 188–190◦C. Anal. found: C, 77.6; H, 6.1%; C29H27OP.1.5 H2O
(MW = 449.5 gr). Calc.: C, 77.5; H, 6.68%.
Synthsise of [{(p-tolyl)3PCHCOC6H5}.HgCl2]2
A solution of 0.14 gr (0.5 mmol) of mercury (II) chloride in dry
methanol (10 mL) was added to a methanolic solution of 0.211 gr (0.5
mmol) of ylide in dry methanol (10 mL). The white product formed
by the slow evaporation of the solvent and dried in vacuum. Yield
0.347 gr (80.11%). m.p. 200–201◦C. Anal. fund: C, 48.3; H. 4.1%;
C29H27OPHgCl2H2O (MW = 711.59). Calc.: C, 48.91; H, 4.07%.
Synthsise of [{(p-tolyl)3PCHCOC6H5}.HgBr2]2
A solution of 0.211 gr(0.5 mmol) of the ylide in dry methanol (10 mL)
was added to 0.18 gr of mercury (II) bromide in dry methanol (10 mL)
and the mixture was stirred for 4 h. The solvent was then removed in
vacuo. The white product obtained was washed with ice-cold methanol
and dried in vacuum. Yield 0.294 gr (75.15%). m.p. 193–195◦C. Anal.
found: C, 43.5; H, 3.7%; C29H27OPHgBr2.H2O (MW = 800.39). Calc.: C,
43.48 H, 3.62%.
Synthsise of [{(p-tolyl)3PCHCOC6H5}.HgI2]2
A solution of 0.211 gr (0.5 mmol) of the ylide in methanol (10 mL)
was added to a solution of 0.227 gr (0.5 mmol) of mercury (II) io-
dide in methanol (10 mL). On concentration by removing the sol-
vent in vacuum, a pale yellow, light-sensitive crystalline solid was
obtained. The crystals were washed with benzene and dried in
vacuo. Yield 0.307 gr (70.2%). m.p. 200–202◦C. Anal. found: C, 37.3;
H, 3.4%; C29H27OPHgI2.2H2O (MW = 912.39). Calc.: C, 38.14; H,
3.39%.
TABLE I υ (CO) of Selected Compound (I) and
Their Complexes With Mercury (II) Halides
Compound
υ (CO)cm−1
Ref.
Ph3PCHCOCH3 (APPY)
Ph3PCHCOPh (BPPY)
Ph3PCHCO (p-tolyl)3
C-coordination
1530
1525
1528
12
12
This article
BPPY.HgCl2
BPPY.HgBr2
[Ph3PCHCO(p-tolyl)3HgCl2]2
[Ph3PCHCO(p-tolyl)3HgBr2]2
[Ph3PCHCO(p-tolyl)3HgI2]2
1635
1630
1597
1633
1597
12
12
This article
This article
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450
S. J. Sabounchei et al.
FIGURE 1 1H NMR {(p-tolyl)3PCHCOC6H5} in CDCl3 at 25◦C.
RESULTS AND DISCUSSION
The υ (CO), which is sensitive to complexation, occurs at 1528 cm−1 in
the parent ylide, as in the case of other resonance stabilized ylides. Coor-
dination of the ylide through carbon causes an increase in υ (CO) while
for O-coordination a lowering of υ (CO) is expected. The IR absorption
FIGURE 2 1H NMR {(p-tolyl)3 PCHCOC6H5.HgCl2}2 in CDCl3 at 25◦C.

New Benzoyl Methylene Triparatolylphosphorine Ylide
451
TABLE II 1H and 31PNMR Data of (I) and Its Complexes With
Mercury(II) Halides. s-singlet; d-doublet; m-multiplet; br-broad
1HNMR
Compound
δ(CH)
2J(P−H)
δPh
31PNMR
Ph3PCHCO(p-tolyl)3
4.4(d)
24.39
—
—
7.3–7.95(m)
7.26–8.13(m)
7.25–8.01(m)
7.52–8.06(m)
12.98(s)
24.4(s)
22.22(s)
18.5(s)
[Ph3PCHCO(p-tolyl)3.HgCl2]2
[Ph3PCHCO(p-tolyl)3.HgBr2]2
[Ph3PCHCO(p-tolyl)3.HgI2]2
5.54(br)
5.2(br)
5.29(br)
—
In CDCl3. 90 MHz. values (ppm) are relative to internal TMS and external 85%
phosphoric acid.
bands observed for the three complexes at 1597, 1633, and 1597 cm−1
indicate coordination of the ylide through carbon. The υ (P+ C−), which
is also diagnostic of the coordination, occurs at 879 cm−1 in (p-tolyl)3P+
CH (Table I). These assignments were confirmed by comparing the
IR spectra of the corresponding 13C substituted ylides.12 In the present
study, the υ(P+ C−) values for all three complexes were shifted to lower
frequencies and observed at 805 cm−1 for three complexes, suggesting
some removal of electron density in the P C bond.
1
In the H NMR spectra for three complexes, the CH ylide proton
shifted downfield compared to that of the free ylide (Figures 1 and 2) as
a consequence of the inductive effect of the metal center. The expected
TABLE III 13CNMR Data of Benzoylmethelenparatolylephosphoran
and Corresponding Complexes With Mercury(II) Halides. s-singlet;
d-double; o-ortho; m-meta; p-para; i-ipso carbon. Recorded in CDCl3
Compound
Ph3PCHCO(p-tolyl)3
Complex (I)
Complex (II) Complex (III)
3CH3
22.2(s)
51.8(d)
113
22.2(s)
22.18(s)
22.22(s)
44.15(s)
CH
—
—
2J(p−c)
CO Ph(o)
CO Ph(m)
CO Ph(p)
CO Ph(i)
P-(p-tolyl)3(o)
2J(p−c)
127.38(s)
128.13(s)
133.63(s)
142.58(s)
132.5(d)
10.6
129.57(d)
12.25
130.67(s)
124.49(d)
95.6
119.3(s)
119.87(s)
133.91(s)
145.48(s)
133.99(d)
10.5
131.1(d)
13
129.48(s)
129.21(s)
119.89(s)
120.62(s)
132.53(s)
145.13(s)
134.02(d)
10.5
130.95(d)
13
133.18(s)
128.95(s)
117.87(s)
118.6(s)
134.88(s)
146.34(s)
133.83(d)
10.6
131.38(d)
13
129.56(s)
128.92(s)
P-(p-tolyl)3(m)
3J(p−c)
P-(p-tolyl)3(p)
P-(p-tolyl)3(i)
1J(p−c)
CO
184.93(s)
193.93(s)
192.41(s)
192.89

452
S. J. Sabounchei et al.
downfield shifts of the 31P and 1H singles for the PCH group upon com-
plexation were observed in their corresponding spectra (Figures 1 and
2, Table II). The appearance of single signals for the PCH group in the
31P and 1HNMR spectra indicates the presence of only one molecule for
all three complexes, as expected for C-coordination.
The 13CNMR data of the complexes and the title ylide are listed in
Table III along with possible assignments. The 13CNMR shifts of the
CO group in the complexes are around 190 ppm, lower than 184 ppm
noted for the same carbon in the parent ylide, indicating a much lower
shielding of carbon of the CO group in the complexes.
REFERENCES
[1] A. W. Johnson, W. C. Kaska, K. A. O. Starzewski, and D. A. Dixon, Ylides and Imines
of Phosphorus (John Wiley and Sons, New York, 1993), Chap. 14 and references given
therein.
[2] M. E. Jung and S. A. Abrechet, J. Org. Chem., 53, 423 (1988).
[3] J. Buckle, P. G. Harrisson, T. J. King, and J. A. Richardes, J. Chem. Soc. Chem.
Commun., 1104 (1972).
[4] J. Buckle and P. G. Harrison, J. Organomet. Chem., 49, C17 (1973).
[5] I. Kawafune and G. Matsubayashi, Inorg. Chem. Acta, 70, 1 (1983).
[6] R. Uson, J. Fornies, R. Navarro, P. Espinet, and C. Mendivil, J. Organomet. Chem.,
290, 125 (1985).
[7] J. A. Albanese, D. A. Staley, A. L. Rheingold, and J. L. Burmeister, Inorg. Chem., 29,
2209 (1990).
[8] S. J. Sabounchei and K. Karami, Phosphorus, Sulfur, and Silicon, 178, 1559 (2003).
[9] H. Koezuka, G. Matsubayashi, and T. Tanaka, Inorg. Chem., 15, 417 (1976).
[10] G. Fronza, P. Bravo, and C. Ticozzi, J. Organomet. Chem., 157, 299 (1978).
[11] (a) K. W. Baure, R. S. Chung, and H. C. Glockner, P. U. S. Patent 3647914, (1969);
(b) K. W. Mason, and R. F. Glockner, P. U. S. Patent 3647914, (1972).
[12] M. Kalyanasundari, K. T. Panchanatheswaran, and R. Huowen, J. Organomet.
Chem., 491, 403 (1995).