Bisaryldithiophosphonic acids: Synthesis and their reactions with organyl chlorosilanes, germanes, stannanes, and plumbanes

Article abstract of DOI:10.1080/10426500902930142

A method of synthesizing arylbisdithiophosphonic acids was developed by the reaction of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with tri(ethylene glycol) and 1,4-butandiol in anhydrous benzene suspension under mild conditions. The arylbisdithiophosphonic acids thus obtained were transformed into the corresponding diammonium salts. New bis(triorganylgermyl), stannyl and plumbyl, and cyclic diphenylsilyl and diphenylplumbyl derivatives of arylbisdithiophosphonic acids were prepared from the reactions of diammonium salts of the corresponding acids with triorganylchlorogermane, chlorostannane, chloroplumbane, diphenyldichlorosilane, and diphenyl dichloroplumbane.

Full text of DOI:10.1080/10426500902930142

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Phosphorus, Sulfur, and Silicon and the
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Bisaryldithiophosphonic Acids: Synthesis
and Their Reactions with Organyl
Chlorosilanes, Germanes, Stannanes, and
Plumbanes
Il'yas S. Nizamov a b , Gulnara T. Gabdullina a b , Ilnar D. Nizamov
a b , Yevgeniy N. Nikitin a b , Lyubov A. Al'metkina c & Rafael A.
Cherkasov c
a A. E. Arbuzov Institute of Organic and Physical Chemistry , Russian
Academy of Sciences , Kazan, Russia
b Tatar State Humanitarian Pedagogical University , Kazan, Russia
c Kazan State University , Kazan, Russia
Published online: 23 Mar 2010.
To cite this article: Il'yas S. Nizamov , Gulnara T. Gabdullina , Ilnar D. Nizamov , Yevgeniy N. Nikitin ,
Lyubov A. Al'metkina & Rafael A. Cherkasov (2010) Bisaryldithiophosphonic Acids: Synthesis and Their
Reactions with Organyl Chlorosilanes, Germanes, Stannanes, and Plumbanes, Phosphorus, Sulfur, and
Silicon and the Related Elements, 185:4, 732-742, DOI: 10.1080/10426500902930142
To link to this article: http://dx.doi.org/10.1080/10426500902930142
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Phosphorus, Sulfur, and Silicon, 185:732–742, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500902930142
BISARYLDITHIOPHOSPHONIC ACIDS: SYNTHESIS AND
THEIR REACTIONS WITH ORGANYL CHLOROSILANES,
GERMANES, STANNANES, AND PLUMBANES
Il’yas S. Nizamov,1,2 Gulnara T. Gabdullina,1,2
Ilnar D. Nizamov,1,2 Yevgeniy N. Nikitin,1,2
Lyubov A. Al’metkina,3 and Rafael A. Cherkasov3
1A. E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy
of Sciences, Kazan, Russia
2Tatar State Humanitarian Pedagogical University, Kazan, Russia
3Kazan State University, Kazan, Russia
A method of synthesizing arylbisdithiophosphonic acids was developed by the reaction
of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with tri(ethylene glycol) and 1,4-
butandiol in anhydrous benzene suspension under mild conditions. The arylbisdithiophos-
phonic acids thus obtained were transformed into the corresponding diammonium salts. New
bis(triorganylgermyl), stannyl and plumbyl, and cyclic diphenylsilyl and diphenylplumbyl
derivatives of arylbisdithiophosphonic acids were prepared from the reactions of diammo-
nium salts of the corresponding acids with triorganylchlorogermane, chlorostannane,
chloroplumbane, diphenyldichlorosilane, and diphenyl dichloroplumbane.
Keywords Bisdithiophosphonic acids; chlorogermanes; chloroplumbanes; chlorosilanes;
chlorostannanes; 1,3,2,4-dithiadiphosphetane-2,4-disulfides; glycols
INTRODUCTION
There is a considerable interest in group 14 element derivatives of pentavalent
phosphorus thioacids containing the P(S)S-E (E = Si, Ge, Sn, Pb) structural fragments
due to their biological activity, because of their high reactivity and their use as syn-
thetic intermediates in the preparation of new organothiophosphorus compounds.1–19 S-
Organosilyl and S-germyl dithiophosphates and heterocycles were obtained in the re-
actions of ammonium dithiophosphoric acids with organochlorosilanes and organoger-
manium mono- and dichlorides.5–8 The common methods of synthesizing S-organotin
dithiophosphates, dithiophosphinates, and tetrathiophosphates were usually based on the
reactions of the corresponding pentavalent phosphorus thioacids or their salts with organ-
otin halides (also in the presence of β-diketones), oxides, hydroxides, tetraalkyltin,
and tributyltin isocyanates.3,4,9–14 Bis(trimethylstannyl) tert-butyltrithiophosphonate
Received 14 November 2007; accepted 2 February 2008.
Dedicated to Professor Marian Mikolꢀajczyk, CBMiM PAN in Lꢀ o´dz´, Poland, on the occasion of his 70th
birthday.
Address correspondence to Rafael A. Cherkasov, Chair of Polymer and Organoelement Compounds, Kazan
State University, Kremlievskaya Str., 18, Kazan, 420008, Russia. E-mail: rafael.cherkasov@ksu.ru
732

BISARYLDITHIOPHOSPHONIC ACIDS
733
was obtained by the reaction of 2,4-bis(tert-butyl)-1,3,2,4-dithiadiphosphetane-2,4-
disulfide with bis(trimethylstannyl)sulfide.15 Triphenyl and diphenyllead(IV) O,O-
alkylenedithiophosphates were prepared similarly in reactions of corresponding dithio-
phosphoric acids.16–19
Over the past several years, we have been involved in the development of alternate
methods of synthesizing organosilicon, germanium, tin, and lead derivatives of pentavalent
phosphorus thioacids using tetraphosphorus decasulfide and 1,3,2,4-dithiadiphosphet-
ane-2,4-disulfides. S-Trimethylsilyl, S-triphenyl, or trialkylgermyl esters of dialkyl
dithiophosphoric and tetrathiophosphoric, 4-methoxyphenyldithiophosphonic, and
trithiophosphonic acids were easily obtained in reactions of tetraphosphorus decasulfide
or Lawes son’s reagent with trimethyl (alkoxy) silanes or trimethyl(alkylthio)silanes,
triphenyl or trialkyl(alkoxy) germanes, and with (alkylthio)germanes.20,21 Reactions
of tetraphosphorus decasulfide or Lawesson’s reagent with trialkyl(alkoxy)stannanes,
with (alkylthio) stannanes, and with bis(trialkylstannyl)sulfide result in the formation of
S-trialkylstannyldialkyldithiophosphates, S-trialkylstanny-ltetrathiophosphates, tris(trial
kylstannyl)tetrathiophosphates, S-trialkylstannyl-(4-methoxyphenyl)dithiophosphonates,
and trithiophosphates, respectively.22–29 Reactions of 2,4-diaryl-1,3,2,4-dithiadiphos
phetane-2,4-disulfides with alkoxy or alkylthiotriorganylplumbanes yielded also the tri-
organolead derivatives of aryldithiophosphonic and trithiophosphonic acids.28,30 In this
article, a facile method of synthesizing new organosilicon, germanium, tin, and lead deriva-
tives of bisaryldithiophosphonic acids is presented.
RESULTS AND DISCUSSION
We have previously prepared the first representatives of bisalkyldithiophosphonic
acids from the reaction of 2,4-dimethyl-1,3,2,4-dithiadiphosphetane-2,4-disulfide with
alkylene glycols in 1:1 molar ratio in diethyl ether suspension at room temperature.31 In
1968, G. Schumacher studied a reaction of Lawesson’s reagent with ethylene glycol in ace-
tonitrile giving rise to O-(2-hydroxyethyl)-4-methoxyphenyldithiophosphonate and O,O-
(1,2-ethylene)bis(4-methoxyphenyl)dithiophosphonic acids.32 However, these compounds
were not isolated in pure form. Meanwhile, it was reported that Lawesson’s reagent and its
4-phenoxy homologue react with 1,2-ethanediol and its substituted derivatives and with 1,4-
butanediol at 70–80◦C for 10–12 h in acetonitrile as a solvent to give the mixture of 1,3,2-
dioxaphosphorinane-2-sulfide, cyclic aryltrithiopyrophosphonate, and thioacetamide.33,34
These compounds seem to be secondary products formed from arylbisdithiophosphonic acid
as an initial product via the hydrogen sulfide elimination due to the effect of acetonitrile
as sulfur acceptor. Indeed, we have previously shown that bisalkyldithiophosphonic acids
react with acetonitrile to form cyclic alkyltrithiopyrophosphonates and thioacetamide.35
Taking into account the low solubility of Lawesson’s reagent and other 2,4-
diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides in diethyl ether previously used as a
solvent for synthesizing bisalkyldithiophosphonic acids31 and the non-inert properties
of acetonitrile toward pentavalent phosphorus thioacids,35 we have tried to find an inert
solvent appropriate for the preparation of bisaryldithiophosphonic acids. We also deemed
it to be necessary to establish milder conditions and shorter time to prevent undesirable
thermal destructions of an initial product. Anhydrous benzene seems to be the most
appropriate inert solvent for successful synthesis of bisaryldithiophosphonic acids. The
reaction of 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides 1a–c with tris(ethylene
glycol) 2a and 1,4-butandiol 2b in benzene suspension have been found to bring about

734
I. S. NIZAMOV ET AL.
Scheme 1
the formation of alkylenoxy(bisaryl)dithiophosphonic acids 3a–e at 50–60◦C for 1-2 h
(Scheme 1, Tables I–IV).
Bisaryldithiophosphonic acids 3a–e were obtained with high yields. Compounds 3a–
e are colorless, viscous liquids, nonvolatile even under reduced pressure, and stable at room
temperature in anhydrous inert atmosphere. Products 3a–e tend to partially decompose
at high temperature and when a falling-film distillation is used in attempted purification.
Bisaryldithiophosphonic acids 3a–e decomposed when water treatment was used.
On the basis of the 31P NMR spectra, it was established that bisaryldithiophosphonic
acids 3a–e were formed as major phosphorus-containing products with chemical shifts
at δ = 87–89 ppm. Alongside the signals of 3a–e, the 31P NMR spectra of the crude
reaction mixtures also reveal the minor singlet signals at δ = 84.1–83.1 ppm with integral
intensity ratio 13:1. It is noteworthy to study the influence of acetonitrile on the stability
of bisaryldithiophosphonic acids 3. We have found that the 31P NMR spectrum of the
chloroform solution of 3e after addition of acetonitrile and storing at room temperature
for 24 h reveals two signals at δ = 88.9 and 84.1 ppm in ratio 1:1.6. It was assumed that
compound with chemical shift at δ = 84.1 ppm is a secondary product.
1
The structures of 3a–e were confirmed by IR (Table III), H (Table IV), and 31P
1
NMR (Table II), as well as by elemental analyses (Table II). H NMR spectrum of 3c in
CDCl3 solution (Table IV) exhibits a triplet due to the methyl protons of two fragments
CH3CH2O-Ar at δ = 1.44 ppm (3JHH = 7.0 Hz), and a quartet at δ = 4.08 ppm is assigned
to the methylene protons of two CH3CH2O-Ar substituents. The protons of the methoxy
group of two CH3OAr fragments of 3a resonate as a singlet at δ = 3.78 ppm, whereas
the protons of the tert-butyl group of two 3,5-di-tert-butyl-4-hydroxyphenyl substituents
of 3e appear as a inventive singlet at δ = 1.48 ppm. The 1H NMR spectra of 3a, 3b, and
3e also show characteristic resonances due to the presence of OCH2OCH2CH2OCH2O
substituent. Thus, a singlet situated at δ = 3.72 ppm was assigned to the four protons of

BISARYLDITHIOPHOSPHONIC ACIDS
735
Table I Experimental data and yields of the products obtained
Starting compounds
quantity [g (mmol)]
Reaction conditions temp.(◦C),
time (h), volume of C6H6
Product
yield [g (%)]
1a 12.0 (29.7)/2a 4.4 (29.7)
1b 8.0 (18.5)/2a 2.7 (18.2)
1b 8.0 (18.5)/2b 1.7 (18.9)
1c 5.0 (8.3)/2b 0.8 (8.9)
1c 5.0 (8.3)/2a 1.2 (8.1)
3a 7.1 (12.8)/NH3 excess
3e 1.2 (1.6)/NH3 excess
4b 2.0 (2.5)/5a 1.7 (5.0)
4b 2.0 (2.5)/5b 1.0 (5.0)
4b 2.0 (2.5)/5c 2.4 (5.1)
4b 2.0 (2.5)/7a 0.65 (2.6)
4b 2.0 (2.5)/7b 1.1 (2.5)
50/1 20 mL
50/1 20 mL
50–55/2 20 mL
50/1 15 mL
50/1.5 15 mL
20/1 20 mL
20/1 20 mL
80/2 50 mL
80/2 50 mL
80/2 50 mL
80/1 40 mL
80/2 60 mL
3a 10.0 (61)a
3b 4.5 (42)a
3c 6.8 (70)a
3d 4.1 (71)a
3e 4.8 (77)a
4a 6.6 (88)b
4b 1.2 (96)b
6a 2.5 (68)a
6b 1.4 (52)a
6c 3.0 (72)b
8a 1.7 (71)a
8b 1.9 (68)b
aYield of crude product.
bYield of solid product.
two central methylene groups COCH2CH2OC of 3e. The methylene protons connected to
the phosphorus atom through the methylene bridge OCH2CH2OP appear as a triplet at δ =
3.84 ppm (3JHH = 4.7 Hz) of 3e. A doublet of triplets observed at δ = 4.39 ppm in the 1H
NMR spectrum of 3e has been assigned to the protons of the methylene group linked with
the phosphorus atom via the oxygen atom CH2CH2OP (3JHH = 4.7 Hz, 3JPH = 10.0 Hz).
Bands in the region ν 2551–2649 and 2475–2396 cm−1 in the IR spectra of 3a–d (Table III)
are due to the valence vibrations of the S H bonds-free and bonded ones, respectively. The
electron impact mass spectrum of 3c exhibits the mass peaks m/e 522 due to its molecular
ion [M]+. (calculated molecular mass M of 3c is 522.1).
Taking into account the rather high thermal stability of the ammonium salts of
pentavalent phosphorus thioacids,3 we decided to prepare the corresponding ammonium
salts using bisaryldithiophosphonic acids 3. The formation of these ammonium salts as
crystalline solids could be expected. In fact, the corresponding ammonium salts 4a,b as
white powders with sharp melting points were obtained by passing anhydrous gaseous
ammonia via the benzene solutions of 3a,e at room temperature (Scheme 2, Tables I–IV).
Scheme 2

736

BISARYLDITHIOPHOSPHONIC ACIDS
737
Table III IR Spectroscopic data of the products obtained
ν, cm−1
3a
3b
3050 ν ( C H, Ar); 2941, 2884 ν (CH3 as, s; CH2 as, s); 2500 (S H, free), 2475 (S H, bonded), 1595,
1569, 1501 ν (C C, Ar), 1026 ν [(P)O C]; 961 ν (C O), ν (C
(C S), 534 ν (P S).
O C), 681, 663 ν (P S), 620 ν
3065 ν (
C H, Ar); 2979, 2935, 2879 ν (CH3 as, s; CH2 as, s); 2550 ν (S H, free); 2430 ν (SH,
bonded); 1596, 1501 ν (C C, Ar); 1041 ν [(P)O C]; 956 ν (OC C); 830 ν (P OC); 695 ν (P S);
537 ν (P S).
3c
3089 ν (
(C C, Ar); 1041 ν [(P)O C]; 971 ν (OC C); 828 ν [P OC]; 694 ν (P S); 537 ν (P S).
3622 ν (OH); 3161, 3089 ν ( H, Ar); 2954, 2924, 2872 ν (CH3 as, s; CH2 as, s); 2549 ν (S H, free);
C H, Ar); 2979, 2938, 2887 ν (CH3 as, s; CH2 as, s); 2551 ν (SH, free); 1596, 1501, 1475 ν
3d
C
2396 ν (S H, bonded); 1583, 1467 ν (C C, Ar); 1050 ν [(P)O C]; 898 ν (P OC); 655 ν (P S); 505
ν (P S).
3e
3619 ν (O H); 2958, 2873 ν (CH3 as, s; CH2 as, s); 2478 ν (S H free); 1582, 1480 ν (C C, Ar); 1429 δ
(CH3 as); 1036 ν [(P)O C]; 957 ν (OC C); 656 ν (P S); 504 ν (P S).
3222 ν (N+H4); 1595, 1497 ν (C C, Ar); 1067 ν [(P)O C]; 952 ν (OC C); 676 ν (P S); 529 ν (P S).
3634 ν (O H); 3230 ν (N+H4); 1581, 1459 ν (C C, Ar); 1427 δ (CH3 as, s); 1068, 1044 ν [(P)O C];
949 ν (OC C); 683 ν (P S); 507 ν (P S).
4aa
4ba
6a
3622 ν (O H); 3068, 3087 ν ( C H, Ar); 2959, 2873 ν (CH3 as, s; CH2 as, s); 1582, 1481 ν (C C,
Ar); 1431 δ (CH3 as); 1036 ν [(P)O C]; 953 ν (OC C); 680, 687 ν (P S); 504 ν (P S); 461 ν
(GePh3 as); 409 ν (Ge-S).
6b
6ca
3622 ν (O H); 3090, 3070, 3034 ν ( C H, Ar); 2959, 2912, 2874 ν (CH3 as, s; CH2 as, s); 1581, 1479
ν (C C, Ar); 1429 δ (CH3 as); 1039 ν [(P)O C]; 951 ν (OC C); 680, 656 ν (P S); 557, 538, 504 ν
(Sn-C as, P S).
3622 ν (O H); 3088, 3061, 3036 ν (
C H, Ar); 2958, 2873 ν (CH3 as, s; CH2 as, s); 1570, 1476 ν
(C C, Ar); 1430 δ (CH3 as); 1036 ν [(P)O C]; 951 ν (OC C); 692, 680 ν (P S); 558, 508 ν (P S);
442 ν (Pb C, PbPh3 as).
8a
3618 ν (O H); 3089, 3070, 3049, 3002 ν (
ν (C C, Ar); 1429 δ (CH3 as); 1035 ν [(P)O C]; 994 ν (OC C); 680 ν (P S); 511 ν (P S, S Si).
3613 ν (O H); 3030 ν ( H); 2923, 2854 ν (CH3 as, s; CH2 as, s); 1572, 1462 ν (C C, Ar); 1035 ν
[(P)O C]; 952 ν (OC C); 654 ν (P S); 564, 523 ν (P S); 478 ν (Pb C, PbPh2).
C H, Ar); 2958, 2874 ν (CH3 as, s; CH2 as, s); 1590, 1479
8ba
C
aIn baseline suspension.
The 31P NMR spectra of salts 4a,b in water solution reveal singlet signals at δ = 107.0
and 109.7 ppm, respectively. The strong broad bands of the valence vibrations of the NH4+
bonds appeared in the range of ν 3222–3220 cm−1 in the IR spectra of 4a,b in baseline
suspension. Bands in the region ν 663–683 and 534–507 cm−1 are due to the valence
vibrations of the P S and P S bonds of 4a,b, respectively. A signal of the S H proton of the
initial acids 3a,e at δ = 2.6 ppm is absent in the 1H NMR spectra of salts 4a,b. The protons
of the HO and NH4 groups of 4b display singlets at δ = 5.43 and 5.45 ppm, respectively.
A mass peak m/e 780.6 was observed in the electron impact mass spectrum of 4b, which
is attributed to its molecular ion [M]+. (calculated molecular mass M of 4b is 780.4).
The diammonium salts of bisaryldithiophosphonic acids seem to be efficient inter-
mediates for synthesizing their organoelement derivatives by substitution reactions with
appropriate organoelement halides. For this purpose, the chlorides of main IV group ele-
ments were used in the reaction with salt 4b. We have found that 4b reacts with triphenyl
chlorogermane 5a, trimethyl chlorostannane 5b, and triphenyl chloroplumbane 5c in ben-
zene at 80◦C for 2 h to give 1,8-bistriorganylgermyl, stannyl, and plumbyl derivatives
of 1,8-triethyleneoxybis(3,5-di-tert-butyl-4-hydroxyphenyldithiophosphonic) acids 6a–c
(Scheme 3, Tables I–IV).

738
I. S. NIZAMOV ET AL.
Scheme 3
Reaction 3 was accompanied by the formation of a powder precipitate of ammonium
chloride, which was removed from the reaction mixture by filtration. Products 6a–c were
obtained with yields of 52–73%. They are viscous under high vacuum nonvolatile oils. The
31P NMR spectra of 6a–c in benzene solutions display singlets in the region of δ = 93.5–
98.7 ppm. These resonances are shifted to low field compared to that of the starting acid
Table IV 1H NMR spectral data of the products obtained
CDCl3, δ, ppm, J, Hz
3a
3b
2.63 m (2H, PSH), 3.70 (s, 4H, COCH2CH2OC), 3.78 (s, 6H, CH3OAr), 3.82 (t, 3JHH7.8, 4H,
OCH2CH2OP), 3.85 (dt, 3JHH7.8, 3JPH 11.2, 4H, OCH2CH2OP), 6.98 (dd, 3JHH9.2, 4JPH3.1, 4H,
3,5-H2C6H2), 7.93 (dd, 3JHH9.2, 3JPH15.9, 4H, 2,6-H2C6H2).
1.40 (t, 3JHH7.0, 6H, CH3CH2OAr); 3.67 (s, 4H, COCH2CH2OC); 3.79 (t, 3JHH4.9, 4H,
OCH2CH2OP), 4.05 (q, 3JHH7.0, 4H, CH3CH2OAr,); 4.33 (dt, 3JHH4.9, 3JPH14.6, 4H,
POCH2CHO2); 6.92 (dd, 3JHH8.6, 4JPH3.4, 4H, 3,5-H2C6H2); 7.90 (dd, 3JHH8.6, 3JHH14.6, 4H,
2,6-H2C6H2).
3c
3e
4b
1.44 (t, 3JHH7.0, 6H, CH3CH2OAr); 3.69 (m, 4H, OCCH2CH2CO); 4.08 (q, 3JHH7.0, 4H,
CH3CH2OAr); 4.21–4.30 (m, 3JHH6.8, 4H, POCH2CCCH2OP); 6.97 (dd, 3JHH8.6, 4JPH3.9, 4H,
3,5-H2C6H2); 7.91 (dd, 3JHH8.6, 3JHH14.6, 4H, 2,6-H2C6H2).
1.48 [s, 36H, (CH3)3C]; 2.37 and 2.64 (m, 2H, S H); 3.72 (s, 4H, COCH2CH2OC); 3.84 (t, 3JHH 4.7,
4H, POCH2CH2O); 4.39 (dt, 3JHH 4.7, 3JPH 10.0, 4H, POCH2CH2O); 5.69 (m, 2H, O H); 7.82
(d, 3JPH 16.2, 2H, C6H2P).
1.47 [s, 36H, (CH3)3C]; 3.59 (t, 3JHH 4.1, 4H, POCH2CH2O); 3.65 (s, 2H, COCH2CH2OC); 3.82 (m,
3JHH 4.4, 4H, POCH2CH2); 5.43 and 5.45 (s, 8H, NH4+; 2H, OH); 7.94 (d, 3JPH 15.1, 2H, C6H2P);
7.96 (d, 3JPH 15.4, 2H, C6H2P).
6a
6b
1.51 [s, 36H, (CH3)3C]; 3.76 (s, 4H, COCH2CH2OC); 3.88 (t, 4H, POCH2CH2O); 4.27 (m, 4H,
POCH2CH2); 5.65 (m, 2H, O H); 7.50 and 7.73 [m, 30H, (C6H5)3Ge]; 7.93 (d, 3JPH 15.5, 4H,
C6H2P).
0.66 [s, d, 2J118Sn−Me56.4, 18H, (CH3)3Sn]; 1.49 [s, 36H, (CH3)3C]; 3.69 (s, 4H, COCH2CH2OC);
3.79 (t, 3JHH 5.0, 4H, POCH2CH2O); 4.22 (dt, 3JHH 5.2, 3JPH 9.5, 4H, POCH2CH2,); 5.63 (m, 2H,
O
H); 7.87 (d, 3JPH 15.9, 2H, C6H2P).
6c
8a
1.49 [s, 36H, (CH3)3C]; 3.64 (m, 4H, POCH2CH2O); 4.07 (m, 3JHH 4,5, 4H, POCH2CH2O); 5.61 (m,
2H, O H); 7.55, 7.73 and 7.86 [m, 30H, (C6H5)3Pb]; 7.86 (d, 3JPH 20.4, 4H, C6H2P).
1.49 [s, 36H, (CH3)3C]; 3.74 (s, 4H, COCH2CH2OC); 3.85 (t, 3JHH 5.2, 4H, POCH2CH2O); 4.40 (dt,
3JHH 5.2, 3JPH 10.5, 4H, POCH2CH2O); 5.69 (m, 2H, OH); 7.41–7.43 and 7.64–7.80 [m, 10H,
(C6H5)2Si)]; 7.85 (d, 3JPH = 16.2, 4H, C6H2P).
8b
1.48 [s, 36H, (CH3)3C]; 3.76 (s, 4H, COCH2CH2OC); 3.92 (t, 3JHH 5.2, 4H, POCH2CH2O); 4.47 (dt,
3JHH 5.2, 3JPH 11.4, 4H, POCH2CH2O); 5.58 (m, 2H, O H); 7.43, 7.56 and 7.75 [m, 10H,
(C6H5)2Pb]; 7.86 (d, 3JPH 16.2, 4H, C6H2P).

BISARYLDITHIOPHOSPHONIC ACIDS
739
3e (δ = 88.9 ppm). This effect indicates a bidentate coordination of the bisaryldithiophos-
phonicligands to thetinand leadatoms similar tothechelatingproperties of dithiophosphato
ligands toward tin and lead atoms.36–38 The IR spectra of 6a–c confirmed the absence of
the bands of the valence vibrations of the NH+4 bonds attributed to salt 4b. The IR spectrum
of the lead-containing derivate 6c exhibits a strong band at ν 442 cm−1 due to the valence
vibrations of the bonds in the PbPh3 group. This band appears in practically the same
region as that for the valence vibrations of the bonds in the GePh3 group of the germanium
compound 6a (ν 461 cm−1). Bands of the valence vibrations of the Sn-C bonds are mixed
with those of the P S bonds and appeared in the range of ν 504 cm−1 in the case of the tin
product 6b. The protons of two trimethylstannyl groups (CH3)3Sn in the 1H NMR spectrum
in CDCl3 solution of 6b appear as an intense singlet at δ = 0.66 ppm as well as a doublet
satellite signal with small intensity and with coupling constant 2J119Sn−Me = 56.4 Hz. The
singlet with double intensity at δ = 1.48 ppm was assigned to the protons of four tert-butyl
groups of aryl substituents. The aromatic protons of two 3,5-di-tert-butyl-4-hydroxyphenyl
substituents of 6b give the typical doublet at δ = 7.87 ppm (3JPH = 15.9 Hz).
The formation of cyclic products could be expected in the case of 14 group element
dichlorides in the reactions with bisaryldithiophosphonic acids or their salts. Indeed, cyclic
diphenylsilyl and diphenylplumbyl derivatives of 1,8-triethyleneoxybis(3,5-di-tert-butyl-
4-hydroxyphenyldithiophosphonic) acids 8a,b were formed in the reaction of 4b with
diphenyl dichlorosilane 7a and diphenyl dichloroplumbane 7b at 80◦C for 1–2 h in benzene
with the precipitation of ammonium chloride (Scheme 4, Tables I–IV).
Scheme 4
The silylated product 8a is an oily liquid, whereas the lead compound 8b is formed as
a colorless crystalline solid with sharp melting point. The 31P NMR spectrum of the silicon
containing product 8a in benzene solution (Table II) displays a singlet at δ = 91.0 ppm.
As we can see, the 31P NMR spectral signal of 8a shows no significant change compared
to that of the starting acid 3e (δ = 88.9 ppm). In the case of plumbyl derivative 8b, its 31P
signal in benzene solution is shifted to lower field (δ = 100.1 ppm) in comparison with
that of acid 3e and its silicon analogue. Thus, the observed tendency for a low field shift
of the 31P resonances of the isostructural arylbisdithiophosphonic derivatives of the group
14 elements increases when passing from the top to the bottom of this group. Moreover,
isostructural arylbisdithiophosphonic derivatives of the silane 8a and the plumbane 8b have
similar signal pattern in the 1H NMR spectra (Table IV); the resonances of the plumbane
8b are shifted to low field in comparison to those of the corresponding silane 8a, however.
The band at ν 654 cm−1 in the IR spectrum of plumbane 8b (Table III) is assigned to the
P S valence vibrations showing a shift to lower frequency with respect to silane 8a (ν P S

740
I. S. NIZAMOV ET AL.
680 cm−1) that also suggests a chelating behavior of the arylbisdithiophosphonic ligands
in the case of tin and lead derivatives.
Thus, the above substitution reactions of diammonium salts of arylbisdithiophospho-
nic acids with organyl chlorosilanes, germanes, stannanes, and plumbanes have a funda-
mental significance as they lead to new types of silicon, germanium, tin, and lead derivatives
of pentavalent phosphorus thioacids containing the P(S)S-E (E = Si, Ge, Sn, Pb) struc-
tural fragments. Moreover, the reactions studied are of interest from the point of view of
preparative organophosphorus chemistry.
EXPERIMENTAL
31P NMR spectra were recorded with a Bruker CXP-100 (36.47 MHz) instrument in
C6H6 with 85% H3PO4 as an external reference. The 1H NMR spectra were obtained with
a Bruker Avance-600 spectrometer (600 MHz) in CDCl3. The IR spectra were obtained in
KBr pellets with a Bruker Vector-22 infrared spectrophotometer. Mass spectra (EI, 60 eV)
were measured with a Finnigan MAT-212 mass-spectrometer.
1,8-Triethyleneoxybis(4-methoxyphenylphosphonic) Acid 3a
A suspension of 1a (12.0 g, 29.7 mmol) and 2a (4.4 g, 29.7 mmol) in 20 mL of
anhydrous benzene was stirred for 1 h at 50◦C. The mixture was filtered. The precipitate
was washed by 5 mL of benzene. The filtrate was evacuated (0.5 mm Hg) at 40◦C for 1 h
and then kept under vacuum (0.02 mm Hg) at 40◦C for 1 h to yield 10.0 g (61%) of crude
3a (see Tables I–IV).
Products 3b–e were obtained similarly (see Tables I–IV).
Diammonium Salt of 1,8-Triethyleneoxybis
(4-methoxyphenylphosphonic) Acid 4a
Excess of anhydrous gaseous ammonium was passed through the solution of 3a
(7.1 g, 12.8 mmol) in 20 mL of anhydrous benzene for 1 h. The mixture was stored at
∼20◦C for ∼12 h and filtered. The precipitate was washed by 20 mL of benzene and dried
under reduced pressure (0.02 mm Hg) at 40◦C for 2 h to give 6.6 g (88 %) of 4a (see Tables
I–IV).
Compound 4b was obtained similarly (see Tables I–IV).
1,8-Bis(triphenylgermyl) Ester of 1,8-Triethyleneoxybis
(4-methoxyphenylphosphonic) Acid 6a
Compound 5a (1.7 g, 5.0 mmol) was added in portions under dry argon with stirring
at 20◦C to the suspension of 2.0 g (2.5 mmol) of 4b in 50 mL of anhydrous benzene, and
stirring was continued for 2 h at 80◦C. The mixture was filtered. The filtrate was evaporated
under vacuum (0.5 mm Hg) at 40◦C for 1 h and then under vacuum (0.02 mm Hg) at 40◦C
for 1 h to give 2.5 g (68%) of 6a (see Tables I–IV).
Compounds 6a, 6b, 8a, and 8b were obtained similarly (see Tables I–IV).

BISARYLDITHIOPHOSPHONIC ACIDS
741
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