Cyclophosphites from oligomethylenephenols

Article abstract of DOI:10.1023/A:1020430206758

New types of oligomethylenephenol cyclophosphites containing 1-3 phosphorus atoms are synthesized by reactions of available oligomethylenephenols with phosphorous acid amides. Contrary to their simple analogs, the resulting phosphites are stable on handling, which allowed design on their basis of complex coordination systems holding promise for metal complex catalysis.

Full text of DOI:10.1023/A:1020430206758

Russian Journal of General Chemistry, Vol. 72, No. 6, 2002, pp. 903 908. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 6, 2002,
pp. 966 971.
Original Russian Text Copyright
2002 by Nifant’ev, Teleshev, Zhdanov.
Cyclophosphites from Oligomethylenephenols
E. E. Nifant’ev, A. T. Teleshev, and A. A. Zhdanov
Moscow State Pedagogical University, Moscow, Russia
Received June 30, 2000
Abstract New types of oligomethylenephenol cyclophosphites containing 1 3 phosphorus atoms are
synthesized by reactions of available oligomethylenephenols with phosphorous acid amides. Contrary to their
simple analogs, the resulting phosphites are stable on handling, which allowed design on their basis of
complex coordination systems holding promise for metal complex catalysis.
Nowadays phosphorylated oligomethylenephenols
attract both theoretical [1] and practical interest [2].
Proceeding with our previous work in this field [3],
here we synthesized from available diols and triols,
such as 2,2 -dihydroxy-5,5 -dimethyl-1,1 -diphenyl-
methane (I) and 4-methyl-2,6-bis(2-hydroxy-5-
methylbenzyl)phenol (II), a new type of phosphites
and studied their principal chemical properties.
Contrary to diol I, triol II has the third arylene cycle,
and, hence, the second methylene bridge, which
imparts additional conformational lability to this
compound. From published data it follows that such
structures allowed synthesis of catalytic systems with
enhanced activity, for example, in hydroformylation
reactions [4].
from diphenols whose phenyl rings are connected by
alkylene bridges were prepared by Pastor et al. [5] by
means of the acid chloride procedure, but the reaction
products were contaminated with amine hydrochorides.
In the present work we phosphorylated diol I and
triol II with phosphoroamidites, such as propanediyl
diethylphosphoramidite and 2,2-dimethylpropanediyl
diethylphosphoramidite, as well as hexaethylphos-
phorous triamide. Using phosphorous amides enabled
us to obtain purer phosphorylation products. In
addition, phosphorous amides more convenient for
experimentation.
Phosphorylation of diol I occurred under mild
conditions: at 20 25 C for 20 h and at 130 C for
30 50 min.
It should be noted that some diphosphites derived
O
O
O
O
R
P
P
R
O
OH
O
OH
O
O
+ 2Et2NP
R
CH3
CH3
CH3
CH3
I
IIIa, IIIb
.
.
(a),
(b).
R =
The contents of diphosphites IIIa and IIIb
pounds having dioxaphosphorinane cycles with
aromatic substituents [6 8]. We failed to distill
diphosphites IIIa and IIIb in a vacuum and isolated
them by reprecipitation with hexane from dioxane or
ether solutions.
in the postreaction mixtures were close to quantitative.
The 31P NMR spectra of the postreaction mix-
tures contained no other signals as singlets at 124
(IIIa) and 115 ppm (IIIb), characteristic of com-
1070-3632/02/7206-0903$27.00 2002 MAIK Nauka/Interperiodica

904
NIFANT’EV et al.
R
R
R
R
S
S
O
O
O
O
O
O
O
P
O
P
O
P
P
O
O
O
[S]
CH3
CH3
CH3
CH3
IIIa, IIIb
IVa, IVb
Sulfurization of compounds IIIa and IIIb occurs
at a temperature of no higher than 100 C, and the
target products are formed in high yields. They are
either oils [compound IVa] or amorphous powders
284.1 Hz) and one more signal at
15 ppm,
P
characteristic of phosphates. The intensity ratio of
these signals was 1:1. This fact suggests that the
complex formation involves one phosphorus center,
and the complex that forms works as a catalytic
system for oxidation of the second phosphorus atom
of this molecule.
1
[compound IVb]. The H NMR spectra of compounds
IIIa, IIIb, IVa, and IVb contain one set of signals
from each proton group. The IR spectra of these
products gave evidence for the absence of free
hydroxy groups.
Phosphorylation of diol I with hexaethylphos-
phorous triamide at a temperature of no higher than
50 C gives, independently of the reagent ratio, a
single product, 6-(diethylamino)-2,10-dimethyl-12H-
dibenzo[d,g]-1,3,2-dioxaphosphocine (VI).
Phosphites IIIa and IIIb were studied as complex-
forming agents in reaction with acacRh(CO)2. The
complex formation was carried out at 1:2 or 1:1
ligand-to-metal ratios. The reactions of diphosphites
IIIa and IIIb with acacRh(CO)2 at a 1:2 in ligand-
to-metal molar ratio give monosubstituted complexes
Va and Vb containing one metal atom per each
phosphorus center. The reactions were accompanied
by vigorous gas evolution. The P Rh coupling
constant in the 31P NMR spectra of the resulting
NEt2
P
O
O
P(NEt2)3
I
CH3
CH3
complexes was 284.1 Hz,
118.0 ppm, coordination
P
VI
shift
2 ppm, which is characteristic of square-
planar cPomplexes of rhodium with phosphite ligands
[9].
The content of cyclic phosphoramidite VI in the
postreaction mixture is close to quantitative. The 31P
NMR spectrum of the postreaction mixture contained
acacRhCO
acacRhCO
O
P
O
only a singlet at
143.5 ppm, i.e. in a range charac-
P
P
teristic of compounds containing amidophosphocane
cycles with aromatic substituents [10 12].
O
O
O
O
R
R
IIIa, IIIb + acacRh(CO)2
High-vacuum distillation gave compound VI in
60% yield. This product is a white crystalline sub-
stance. Its structure and composition were proved by
physicochemical methods. Compound VI is very
stable even in air. It does not oxidize or hydrolyze
during 100 h at 20 C, and thus can be used as a phos-
phorylating agent. Phosphorylation of diol I with
hexaethylphosphorous triamide at 55 80 C and a 3:2
molar ratio gave 2,2 -[2,2 -methylenebis(4-methyl-1-
phenoxy)]bis[2,10-dimethyl-12H-dibenzo[d,g]-1,3,2-
dioxaphosphocine] (VII). The reaction was complete
CH3
CH3
Va, Vb
The absorption band of the carbonyl group at the
Rh atom in the IR spectrum (2000 cm ) confirms the
composition of the complex. It was isolated by pre-
cipitation with hexane from methylene chloride solu-
tion as yellow fine crystals.
1
When the complex formation was carried out at a in 8 h at 80 C. The 31P NMR spectrum of the post-
1:1 ligand-to-metal molar ratio, the 31P NMR spec-
trum contained a signal at 118.0 ppm (JPRh
reaction mixture contained only a singlet at
118.8 ppm.
P
P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002

CYCLOPHOSPHITES FROM OLIGOMETHYLENEPHENOLS
905
thylene chloride solution. Its 31P NMR spectrum
CH3
O
CH3
O
CH3
O
CH3
O
contains a doublet at 125.0 ppm (JPRh 302.0 Hz,
P
9.3 ppm), which is characteristic of complexes
with phosphite ligands [9]. The observed charac-
teristics suggest a chelate-type complex formation
between acacRh(CO)2 and compound VII. The IR
spectrum of compound VIII lacked a characteristic
P
P
2P(NEt2)3
O
O
3I
1
carbonyl absorption band at 2000 cm , providing
evidence for chelation.
CH3
O
CH3
CH3
CH3
VII
Compound VII is very stable. Under an inert
atmosphere it may be stored up to 8 months, which is
confirmed by the stability of its spectral characte-
O
acacRh
O
CH3
CH3
P O
PO
ristics ( 118.8 ppm).
P
acacRh(CO)2
VII
In terms of organometallic synthesis, using P(III)
oligomethylenephenols as a ligand surrounding is
absolutely urgent, because, being highly active in
complex formation [presence of P(III)], they are also
very stable (to oxidation and hydrolysis) ligands and
impart stability to their complexes. The complex
formations with diphosphite VII were carried out at
1:2 and 1:1 reagent molar ratios. It was found that,
independently of the ligand-to-metal molar ratio, the
reactions result in exclusive formation of chelate VIII.
It is a yellow finely crystalline powder with a high
decomposition point (174 176 C). Chelate VIII was
isolated by reprecipitation with hexane from a me-
O
CH3
CH3
VIII
Phosphorylation of triol II with cyclic phosphorous
acid amides proceeds under mild conditions at 20
25 C.
R
O
O
O
O
O
O
R
P
P
R
P
O
O
O
OH
OH
OH
O
O
+ 3Et2NP
R
CH3
CH3
IXa, IXb
CH3
CH3
CH3
CH3
II
.
.
R =
(a),
(b).
The contents of triphosphites IXa and IXb in the
postreaction mixtures were close to quantitative. The
31P NMR spectra of these mixtures contained two
signals at 119.3 and 115.0 ppm, characteristic of
compounds having dioxaphosphorinane cycles with
aromatic substituents. Note that the integral intensity
ratio of the signals of two terminal phosphorus centers
and the internal one is 2:1.
Sulfurization of phosphites IXa IXb gave corres-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002

906
NIFANT’EV et al.
R
R
R
R
R
R
S
S
S
O
O
O
O
O
O
O
O
O
O
O
O
P
O
P
O
P
P
P
P
O
O
O
O
[S]
t
CH3
CH3
CH3
CH3
CH3
CH3
IXa, IXb
Xa, Xb
ponding thio derivatives X. It is noteworthy that in
the 31P NMR spectrum of compounds Xa and Xb the
integral intensity ratio of the signals belonging to
internal and terminal phosphorus centers remains
equal to 1:2. The composition, structure, and indi-
viduality of the obtained compounds were confirmed
by physicochemical methods.
pectrum contained two doublets at
119.4 (ter-
P
minal) and 123.2 ppm (internal). The integral intensity
ratio of these signals was 2:1. The presence of two
doublets in the 31P NMR spectrum is explained by
that ligands IXa and IXb contain three prosphorus
centers: two terminal and one internal. The Rh P
coupling constants for the doublets belonging to
terminal and internal centers are 282.9 and 281.9 Hz,
The reaction Rh(acac)(CO)2 with 2,6-bis(5,5-
dimethyl-1,3,2-dioxaphosphorinan-2-yl)-1-[2-(5,5-
dimethyl-1,3,2-dioxaphosphorinan-2-yloxy)-5-
term
respectively. The coordination shifts
and
P
int
are 8.7 and 8.6 ppm, which is characteristic of
P
complexes with phosphite ligands [9]. The above
characteristics suggest substitution of one of the
carbonyl groups in acacRh(CO2) by the phosphorus-
containing ligand.
methylbenzyl]-4-methylbenzene (IXb) at a 1:3 ligand-
to-metal molar ratio was accompanied by gas evolu-
tion. Reprecipitation with hexane from methylene
chloride solution gave a complex whose 31P NMR
R
acacRhCO
acacRhCO
acacRhCO
R
R
O
O
O
P
P
P
O
O
O
O
O
O
acacRh(CO)2
20 C
IXa, IXb
CH3
CH3
CH3
XIa, XIb
The IR spectrum contains a characteristic carbonyl
absorption band at 1998 cm , which implies that only
Hence, we succeeded in extending the range of
promising ligands for complex formation. Note that
the described ligands and complexes derived from
them are stable compounds.
1
one CO group is substituted. Complex XI is an
amorphous yellow powder (decomp. point 115
118 C). The reactions of compounds IXa and IXb
with acacRh(CO)2 at 1:2 ligand-to-metal ratios
involved no chelate formation. Therewith, the 31P
EXPERIMENTAL
The IR spectra of compounds IIIa, IIIb, Va, Vb
IXa, IXb, XIa, and XIb were recorded on a Specord
IR-75 spectrometer for methylene chloride solutions
NMR spectrum contained a phosphate signal at
P
15 ppm. This is explained by the fact the resulting
complex catalyzes oxidation of phosphorus centers
which have not taken part in complex formation with
acacRh(CO)2.
1
in NaCl cells. The H NMR spectra of compounds I,
II, IIIa, IIIb, VI, VII, IXa, and IXb were recorded
on a Bruker WP-250 spectrometer (250 MHz) in
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002

CYCLOPHOSPHITES FROM OLIGOMETHYLENEPHENOLS
907
CDCl3 against TMS. The 31P NMR spectra of com-
pounds IIIa, IIIb, IVa, IVb, Va, Vb, VI, VII, VIII,
IXa, IXb, XIa, and IXb methylene chloride were
C4,6Ha), 3.82 s (2H, CH2), 4.2 m (4H, C4,6He), 6.85
m (4H, CH2 Ar), 7.0 s (2H, CH2 Ar). Found, %: C
61.18, H 6.51; P 12.60. C25H32O6P2. Calculated, %:
C 61.22; H 6.53; P 12.65.
recorded on
a
Bruker WP-80SY spectrometer
(32.4 MHz) against external 85% phosphoric acid.
6-(Diethylamino)-2,10-dimethyl-12H-dibenzo-
[d,g]-1,3,2-dioxaphosphocine (VI). A mixture of diol
I, 6.6 g, and 7.15 g of hexaethylphosphorous triamide
was heated without solvent at 50 C in a vacuum
(15 mm) for 40 min. The product was isolated by di-
stillation, bp 215 C (5 mm), white solid, yield 60%,
All manipulations were carried out under argon.
Solvents were purified according to known procedu-
res [13]. TLC was carried out on Silufol plates, elu-
ents 1:1 ether hexane (A), 1:1 dioxane benzene
(B), 1:1 benzene hexane (C), 1:2 hexane ether (D),
and 2:1 benzene hexane (E). Development by iodine
vapor or silver nitrate, or by calcination.
1
mp 89 91 C, Rf 0.5 (C). H NMR spectrum (CDCl3),
, ppm: 1.25 t (6H, NCH3CH3), 2.3 s (6H, Ar CH3),
3.333.5 m (4H, NCH2CH3), 3.4 q (2H, CH2), 4.3 q
(2H, CH2), 6.8 7.0 m (4H, Ar), 7.1 s (2H, Ar). 31P
2,2 -Dihydroxy-5,5 -dimethyl-1,1 -diphenylme-
thane (I). p-Cresol, 100 g, and 25 g of a 30%
formaldehyde solution was heated at 50 C for 2 h in
the presence of 2.5 ml of concentrated hydrochloric
acid. Then the reaction mixture was cooled to room
temperature and mixed with 150 ml of benzene. The
precipitate that formed was filtered off, and the filtrate
was distilled. After removal of the solvent, water, and
excess p-cresol, 2,2 -dihydroxy-5,5 -dimethyl-1,1 -di-
phenylmethane was distilled at 240 C (15 mm), mp
NMR spectrum (benzene):
143.5 ppm. Found, %:
P
C 68.4; H 7.01; P 8.98. C19H24NO2P. Calculated, %:
C 69.3; H 7.29; P 9.42.
2,2 -[2,2 -Methylenebis(4-methyl-1-phenoxy)]bis-
[2,10-dimethyl-12H-dibenzo[d,g]-1,3,2-dioxaphos-
phocine] (VII). A mixture of 5 g of diol I, 3.61 g of
hexaethylphosphorous triamide, and 3 ml of benzene
was heated at 80 C for 8 h. After cooling, white
crystals precipitated. Yield 81%, mp 178 180 C, Rf
1
125 126 C, Rf 0.61 (A), 0.5 (B). Yield 15%. H
1
NMR spectrum (CDCl3), , ppm: 2.15 s (6H, CH3),
3.76 s (2H, CH2), 6.65 d (2H, Ar), 6.8 q (2H, Ar),
7.1 s (2H, Ar), 7.4 s (2H, OH).
0.65 (C). H NMR spectrum (CDCl3), , ppm: 2.22 s
(18H, CH3 Ar), 3.8 s (6H, CH2), 6.68 s (6H, Ar),
6.7 s (6H, Ar); 6.8 6.9 q (6H, Ar). 31P NMR spec-
trum: P 118.8 ppm. Found, %: C 71.8; H 5.45; P 8.02.
C45H42O6P. Calculated, %: C 72.9; H 5.67; P 8.37.
2,2 -Bis(1,3,2-dioxaphosphorinan-2-yloxy)-
5,5 -dimethyl-1,1 -diphenylmethane (IIIa). Diol I,
2 g, was treated with 3.2 g of 2-diethylamino-1,3,2-
dioxaphosphorinane and heated at 130 C for
30 min (or at 20 25 C for 20 h). The evolving di-
ethylamine was removed in a vacuum. After cooling,
the reaction mixture was dissolved in dioxane or di-
ethyl ether, and the product was precipitated with
hexane. The precipitate was filtered off and dried at
2,2 -[2,2 -Methylenebis(4-methyl-1-phenoxy)]bis-
(5,5-dimethyl-1,3,2 5-dioxaphosphorinane 2-sul-
fide) (IVb). A mixture of 0.1 g of compound IIIb and
0.013 g of sulfur was heated for 10 h at 80 C. After
cooling, the reaction mixture was dissolved in diethyl
ether, the solution was filtered, and the solvent was
1
removed. Yield 0.071g (71%), Rf 0.68 (B). H NMR
spectrum, , ppm: 0.82 s, 1.26 s (12H, CH3 c), 2.22 s
(6H, CH3 Ar), 3.35 m (4H, C4,6Ha), 3.82 s (2H,
CH2), 4.2 m (4H, C4,6He), 6.85 m (4H, CH2 Ar),
40 C (15 mm). Yield 3.06 g (73%), mp 78 80 C, Rf
1
0.86 (B),
123.5 ppm. H NMR spectrum, , ppm:
0.82 s, 2.2P2 s (6H, CH3 Ar), 3.35 m (4H, C4,6Ha),
3.82 s (2H, CH2), 4.2 m (4H, C4,6He), 6.85 m (4H,
Ar), 7.0 s (2H, Ar). Found, %: C 56.84; H 5.71; P
14.1. C21H26O6P2. Calculated, %: C 57.79; H 5.96;
P 14.22.
7.0 s (2H, CH2 Ar).
31P NMR spectrum:
P
53.94 ppm. Found,%: C 53.1; H 5.8; P 10.7; S 11.1.
C25H32O6P2S2. Calculated,%: C 54.1, H 5.7; P 11.2;
S 11.5.
2,2 -Bis(5,5-dimethyl-1,3,2-dioxaphosphori-
nan-2-yloxy)-5,5 -dimethyl-1,1 -diphenylmethane
(IIIb). Diol I, 2 g, was treated with 3.6 g of phos-
phamide and heated at 130 C for 30 min. The evolv-
ing diethylamine was removed in a vacuum. After
cooling, the reaction mixture was dissolved in diethyl
ether and filtered. The solvent was removed from the
filtrate, and the residue was dried at 40 C (15 mm).
2,6-Bis(1,3,2-dioxaphosphorinan-2-yl)-1-[2-
(1,3,2-dioxaphosphorinan-2-yloxy)-5-methyl-
benzyl]-4-methylbenzene (IXa). A mixture of 2 g of
triol II, 3.05 g of 2-(diethylamino)-1,3,2-dioxa-
phosphorinane, and 5 ml of benzene was kept in a
vacuum for 4 h at 25 C. The solvent was then re-
moved to leave a viscous oil, yield 3.33 g (88%), Rf
1
0.89 (A). H NMR spectrum (CDCl3), , ppm: 2.24 d
Yield 3.06 g (71%), mp 82 83 C, Rf 0.49 (B),
(9H, Ar CH3), 3.82 s (4H, Ar CH2), 3.94 m (9H,
P
2
3
3
1
CH2e, JH H 10.67 Hz), JH P 4.1 Hz, JH P 4.3 Hz),
115.3 ppm. H NMR spectrum, , ppm: 0.82 s, 1.26 s
a
e
a
e
(12H, CH3 c), 2.22 s (6H, CH3 Ar), 3.35 m (4H,
4.15 m (9H, CH2a), 6.67 d (3H, Ar), 6.85 d (2H,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002

908
NIFANT’EV et al.
decomp. point 174 176 C. 31P NMR spectrum:
Ar), 7.05 s (3H, Ar). 31P NMR spectrum, P, ppm:
P
119.3 (internal), 115.0 (terminal); internal/terminal 125.0 ppm (JPRh 302.6 Hz).
signal ratio 1:2.
Complex XIb. To a mixture of 0.174 g of
dicarbonylrhodium acetylacetonate and 5 ml of
benzene, 0.168 g of compound IXb was added. When
CO no longer evolved, the solvent was removed, and
the target compound was precipitated with hexane.
2,6-Bis(5,5-dimethyl-1,3,2-dioxaphosphori-
nan-2-yl)-1-[2-(5,5-dimethyl-1,3,2-dioxaphos-
phorinan-2-yloxy)-5-methylbenzyl]-4-methylben-
zene (IXb). A mixture of 1 g of triol II and 2.28 g of
2,2-dimethylpropanediyl diethylphosphoramidite was
kept in a vacuum (15 mm) for 4 h at 80 C to obtain a
viscous oil, yield 1.72 g (87%), Rf 0.69 (A). 1H NMR
spectrum (CDCl3), , ppm: 0.82 s (9H, CH3), 1.26 s
(9H, CH3), 2.24 d (9H, Ar CH3), 3.82 s (4H,
Yield 0.262 g (81%), yellow powder, decomp. point
1
1980 cm . 31P
115 117 C. IR spectrum: (CO)
NMR spectrum, P, ppm: 123.1 (internal), 119.3
(terminal) (JPRh 281.9 Hz), internal/terminal signal
ratio 1:2.
2
Ar CH2), 3.94 m (9H, CH2e, JH H 10.67 Hz,
a
e
3
3JH P 4.1 Hz, JH P 4.3 Hz), 4.15 m (9H, CH2a),
a
e
REFERENCES
6.67 d (3H, Ar), 6.85 d (2H, Ar), 7.05 s (3H, Ar). 31P
NMR spectrum, P, ppm: 119.3 (internal), 115.0
(terminal); internal/terminal signal ratio 1:2. Found,
%: C 60.2; H 6.72; P 11.8. C38H51O9P3. Calculated,
%: C 61.2; H 6.85; P 12.5.
1. Fedorov, S.G., Cand. (Chem.) Dissertation, Moscow,
1965.
2. Weber, D., Habicher, W.D., Nifant’ev, E.E., Tele-
shev, A.T., and Zhdanov, A.A., Phosphorus, Sulfur
Silicon, 1999, vol. 149, pp. 143 165.
3. Nifant’ev, E.E., Teleshev, A.T., Zhdanov, A.A.,
Bel’skii, V.K., Weber, D., and Habicher, W.D, Dokl.
Ross. Akad. Nauk, 1999, vol. 366, no 2, pp. 202 206.
4. EU Patent 214622, Chem. Abstr., 1987, vol. 107,
25126k.
5. Pastor, S.D., Hyun, J.L., Odorizo, P.A., and Rode-
baugh, R.K., J. Am. Chem. Soc., 1988, vol. 110, no. 8,
pp. 6547 6555.
6. Nifant’ev, E.E., Rasadkina, E.N., Ronkova, E.V.,
Bekker, A.P., Magomedova, N.S., and Bel’skii, V.K.,
Zh. Obshch. Khim., 1994, vol. 64, no. 9, pp. 1448
1454.
2,6-Bis(5,5-dimethyl-2-thioxo-1,3,2 5-dioxa-
phosphorinan-2-yl)-1-[2-(5,5-dimethyl-2-thioxo-
1,3,2-dioxaphosphorinan-2-yloxy)-5-methyl-
benzyl]-4-methylbenzene (Xb). A mixture of 1 g of
IXb and 0.129 g of sulfur was kept at 80 C for 10 h
to obtain a viscous oil, yield 0.98 g (87%), Rf 0.79
1
(A). H NMR spectrum (CDCl3), , ppm: 0.82 s (9H,
CH3), 1.26 s (9H, CH3), 1.26 s (9H, CH3), 2.24 d
(9H, Ar CH3), 3.82 s (4H, Ar CH2), 3.94 m (9H,
2
3
CH2e, JH H 10.67 Hz, JH P 4.1 Hz), 4.15 m (9H,
a
a
CH2a), 6.67ed (3H, Ar), 6.85 d (2H, Ar); 7.05 s (3H,
Ar). 31P NMR spectrum, P, ppm: 55.8 (internal), 53.4
(terminal), internal/terminal signal ratio 1:2. Found,
%: C 53.2; H 5.9; P 10.8; S 10.4. C38H51O9P3S3. Cal-
culated, %: C 54.2; H 6.0; P 11.0, S 11.4.
7. Nifant’ev, E.E., Rasadkina, E.N., Bel’skii, V.K., and
Stash, A.I., Dokl. Ross. Akad. Nauk, 1995, vol. 341,
no. 11, pp. 491 494.
Complex Vb. Dicarbonylrhodium acetylaceto-
nate, 0.0929 g, in 5 ml of methylene chloride was
treated with 0.08858 g of compound IIIb. When CO2
no longer evolved, the solvent was removed, and the
product was precipitated with hexane. Yield 0.14 g
(82%), yellow powder, decomp. point 105 108 C, Rf
8. Rasadkina, E.N., Magomedova, N.S., Bel’skii, V.K.,
and Nifant’ev, E.E., Zh.Obshch. Khim., 1995, vol. 65,
no. 2, pp. 214 222.
9. Nifantyev, E.E., Teleshev, A.T., Grishina, G.M., and
Borisenko, A.A., Phosphorus Sulfur, 1985, vol. 24,
pp. 333 342.
10. Litvinov, I.A., Kataeva, O.N., Naumov, V.A., and
Arshinova, R.P., Izv. Akad. Nauk SSSR, 1987, no. 9,
pp. 1985 1987.
11. Arshinova, R.P., Danilova, S.A., Arbuzov, B.A.,
Phosphorus Sulfur, 1987, vol. 34, pp. 1 12.
12. Arshinova, R.P., Danilova, S.A., and Arbuzov, B.A.,
Phosphorus, Sulfur Silicon, 1992, vol. 68, pp. 155
187.
1
0.43 (A). IR spectrum: (CO) 1990 cm . 31P NMR
spectrum:
119.3 ppm (JPRh 287.0 Hz).
P
[2,2 -[2,2 -Methylenebis(4-methyl-1-phenoxy)]-
bis[2,10-dimethyl-12H-dibenzo[d,g]-1,3,2-dioxa-
phosphocin-2-yl]]rhodium acetyacetonate (VIII).
Compound VII, 0.286 g, was added to a mixture of
0.1 g of dicarbonylrhodium acetylacetonate and 5 ml
of benzene. When CO no longer evolved, the solvent
was removed, and the target compound was precipi-
tated with hexane. Yield 0.3 g (84%), yellow powder,
13. Gordon, A.J. and Ford, R.A., The Chemist’s Compa-
nion, New York: Wiley, 1972.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 6 2002