M. A. Sarukhanov, M. Sh. Mridkha, Yu. Ya. .... RJIR 0,84liiMOJI~ J}:Hra:ap;a B 5-10 llfJI BO,ll,hlii rp. ..... v(Pt-Br) [17] II 330-323cM-1 ;J.JIR v(Pt--N02) [18, 19].
7. 8. 9. 10. 11. 12. 13. 14. 15.
16. 17. 18.
-M. P. Martinez, M. Valcarcel, and F. Pino, Anal. Chim. Acta, 81, No. 2, 176 (1976). Y. K. Bhoon, S. Mitra, J.P. Scovill, and D. L. Klayman, Transition Met. Chern., 7, No.3, 264 (1982). B; Singh and H. Misra, J. Indian Chern. Soc., 63, No. 12, 1069 (1986). J.D. Coordrich, P. N. Nickias, and J.P. Selegue, Inorg. Chern., 26, No. 21, 3424 (1987). A. D. Gamovskii, 0. A. Osipov, L. I. Kuznetsova, and N. I. Bogdashev, Usp. Khim., 42, No.2, 177 (1973). A. D. Gamovskii, 0. A. Osipov, and V. N. Sheinker, Koord. Khim., 6, No. 1, 3 (1980). S. S. Kukalenko, B. A. Bovykin, S. I. Shestakova, and A. M. Omel'chenko, Usp. Khim., 54, No. J, 1152 (1985). J. Reedijk, in: G. Wilkinson, Comprehensive Coordination Chemistry, Vol. 2, Pergamon Press, Oxford (1987), p. 73. N. I. Dorokhova, V. N. Komissarov, A. V. Khokhlov, and A. D. Garnovskii, in: Abstracts of Reports to the 6th All-Union Conference on the Chemistry of Nonaqueous Solutions of Inorganic and Complex Compounds [in RUSSian] Nauka, Moscow (1987). ' D. X. West, P.M. Ahrweiler, G. Ertem, et al., Transition Met. Chern., 10, No. 7, 264 (1985). V. A. Kogan, V. V. Zelentsov, V. V. Lukov, and N. V. Gerbeleu, Zh. Neorg. Khim., 31, No. 11,2844 (1986). V. T. Kalinnikov and Yu. V. Rakitin, Introduction to Magnetochemistry. Determination of the Static Magnetic Susceptibility in Chemistry [in Russian], Nauka, Moscow (1980), p. 255.
BINUCLEAR COMPLEXES OF Pt(II) WITH BRIDGING MOLECULES OF POLYMETHYLENEDIAMINES A. I. Stetsenko, K. I. Yakovlev, N.D. Rozhkova, V. G. Pogareva, and S. A. Kazakov
UDC 541.49:546.922 + 547.415.1
The reactions of trans-[Pt(NH3hX 2] and aliphatic polymethylenediamines (n = 3-6) taken in a Pt:L mole ratio equal to 2:1 give binuclear complexes with bridging molecules of the type trans-[Pt(NH3)zX-L-Pt(NH3hX]X2 , where X= Cl, Br, N02 • The bridging coordination of the diamines has been demonstrated IR-spectroscopically. The acid dissociation constants of the diaquo ions have been determined by a potentiometric method: K 1 = (2.5 ± 0.5)·10-6, K 2 = (2.4 ± 0.3)·10-7 (for n = 6) and K 1 = (2.8 ± 0.6)·10-6, K 2 = (6.1 ± 1.6)·Hr7 (for n = 3). Their analysis reveals the independent character of the titration of the water molecules in the complexes and the practical absence of an influence of the length of the carbon chain on the acid properties of the terminal water molecules.
The most characteristic type of coordination for polymethylenediarnines with the general formula NH2-(CH~,.-NH2 is bidentate chelation with the formation of five- and six-membered rings [1]. There have been a few indications Qf the possibility of the bridging coordination of such ligands in the complexes of platinum with ethylenediamine [2-6] and N,N,N',N'-tetrakis(2-aminoethyl)-1,6-diaminohexane [7, 8]. A number of binuclear complexes of Pt(II) with bridging nitrogen-containing heterocyclic ligands, viz., 2-aminopyrimidine [9], adenosine [1o-12], and uracil [13-15], have been isolated. The probability of the formation of binuclear complexes of Pt(ll) with the bridging bonding of polymethylenediamines increases when Pt(II) complexes with a trans structure are employed as the starting compounds. In the present work we investigated the products of the reactions of trans-[Pt(NH 3nX 2] (X= a-. Br-. N02-) with the following series of aliphatic polymethylenediamines with the general formula NH 2-(CH2),.-NH 2 (L): 1,3-diaminopropane (U), 1,4-diaminobutane (L2), 1,5-diaminopentane (L3), 1,6-diaminohexane (L4). The trans -diacidodiammines of Pt(Ilf emplo)'ed as the starting complexes {[Pt(NH3hC1 2], [Pt{NH3hBr2], and [Pt(NH 3h(N02)Cl]} were synthesized according to known methods [16]. The reaction of trans-[Pt(NH 3nC1 2] with the diamines was carried out with a Pt:L mole ratio equal to 2:1 according to the scheme 2trans-[Pt(NH 3h02l + L..,.. trans-[Pt(NH 3) 2Cl-L-Pt(NHJ)2Q]Q2
(1)
I Leningrad Chemicopharmaceutical Institute.
Translated from Koordinatsionnaya Khimiya, Vol. 16, No. 4, -
~pp. 560-565, April, 1990. Original article submitted May 19, 1988.
300
0364-4626/90/1604-Q300$12.50 Ct991 Plenum Publishing Corporation
•
A 1.67-mole portion of trans-[Pt(NH3hCI2J dissolved in 130 ml of hot water was given an addition of 0.84 mmole of ligand in 5-10 ml of water, and the mixture was heated in a boiling water bath for 7-8 h, during which the original :~loW color. o~ th~ _solution ~came less intense. Then the solution was evaporated to 30-35 ml, cooled by ice, and filtered to · ove the mstgmftcant quanttty of unreacted trans-[Pt(NH 3hC12]. The filtrate was evaporated to 2-3 ml and cooled. At rem point a white precipitate of the reaction product formed, and it was separated from the mother solution and washed with thiS . . . . small quanttty of tee water and ethanol. In order to remove any posstble admtxture of trans-[Pt(NH 3hC1 2], the substance dissolved at room ~emperature in a minim.al quantity of water acidified by one or two drops of HCl, the solution obtained filtered, and the·ftltrate was evaporated tn a water bath to 2-3 ml and cooled. The precipitate of the complex compound "'rmed was filtered out, washed with ethanol, and dried at 80-90·c. The yield was equal to 40-SQ?c;. to In view of the poor solubility of trans- [Pt(NH3hBr2], its reactions with the diamines were carried out by heating ueOUS suspensions of the original complex with the ligands (the Pt:L mole ratio was equal to 2:1). As in the case of the ~loride derivatives, this resulted in the formation of the binuclear complexes trans-[Pt(NH3)2Br-L-Pt(NH3)2Br]Br2 (II) in the form of white precipitates having a yellowish tint with a 40-SQ?c; yield. The binuclear bromide complexes with L 1, L2 , and L4 were also obtained by another method:
:as as
trans-[Pt(NH 3hCl-L-Pt(NH 3)2Cl]Cl2 + 4AgN03 + 2H20 --+ trans-[Pt(NH 3hH2G-L-Pt(NH 3hH 20](N03)4 + 4AgCl, (2) trans-[Pt(NH 3)2H2G-L-Pt(NH3)2H20](N03)4
+ 4KBr--+ transiPt(NH3hBr-L-Pt(NH3hBr]Br2 + 4KN03
(3)
A 0.37-mmole portion of compound I dissolved in 5 ml of water was given an addition of 1.44 mmole of AgN03 in 3 ml of water. and the mixture was held at room temperature in the dark for 24 h. Then the precipitate of AgCl was filtered out. and 1.47 mmole of KBr were added to the filtrate. At this point the solution became cloudy, and a white precipitate of compound II with a yellowish tint gradually formed. After 24 h, the latter was filtered out and washed with ice water and eth3nol. Compound II could be obtained by this method with a 50-6()7o yield. In order to obtain a binuclear nitrito compound with a bridging molecular aliphatic diamine (n = 4-6), rrans-[Pt(NH3hN02CL] was employed as the starting complex. When Pt:L = 2:1, its reaction with solutions of the ligands takes place according to the scheme 2trans-[Pt(NH3h(N02)Cl]
+ L--+ trans-[Pt(NH3hN02-L-Pt(NH3)2N02]Cl2.
(4)
III
A 2.00-mole portion of trans- [Pt(NH3)2N02Cl] was dissolved in 40 ml of hot water, and the solution obtained was given an addition of 1.00 mmole of the ligand in 5-10 ml of water and heated in a boiling water bath over the course of 3 h. At this point the solution became colorless, and precipitation of the original compound was not observed upon cooling. The solution was evaporated to 3-4 ml, cooled, filtered, and given an addition of 40-50 ml of ethanol. The white precipitate of the complex formed was filtered out, washed with ethanol, and dried at 80-90"C. The yield of the product was 7o-8()7o. Binuclear nitrito complexes with bridging molecules of polymethylenediamines can also be obtained by reacting the aquo ion trans-[Pt(NH 3h(N02)H 20:r with the corresponding ligand, as was demonstrated in the example of the reaction with hexamethylenediamine. The complex trans-[Pt(NH 3hN02-NH2-(CH2l6-NH2-Pt(NH 3hN02](N03h was recovered as a· result. All the compounds obtained according to reactions (1)-(4) were analyzed to determine the content of Pt, the halogen, ~. C, and H (Table 1). The molar electrical conductivity of their aqueous solutions is found in the range between 181 and 2.56 n- 1·cm2·mole- 1 and attests to the dissociation of the complexes into three ions. These data (Table 1) allow us to assign the following coordination formulas of the binuclear type with bridging molecules of the aliphatic diamines to the compounds obtained: NHa
NHa
I
I
[X-I't-1'\H,-(CH,)"-NH,-I't-X]X,
•
I
Nlla
I
NH 3
Additional evidence in support of such a structure,for the complexes isolated is provided by the presence of single-line absorption bands corresponding to the stretching vibrations of the Pt-X bonds in their far-infrared spectra at 348-337. cm- 1 for v(Pt-Cl), 251-232 cm- 1 for v(Pt-Br) [17], and 330-323 cm- 1 for v(Pt-N02) [18, 19]. The interpretation of the IR spectra of the compounds isolated·is somewhat complicated by the fact that they contain ammonia molecules having their own characteristic v(NH) and 5(NH2 ) vibrations at 3275-3100 and 1700-1500 cm- 1, respectively. However, the study of theIR spectra of the complexes synthesized still made it possible to trace a number of laws. First, the character of the absorption in the regions of the stretching and deformation vibrations of the amino group is Similar to that observed in the IR spectra of the known binuclear complexes of platinum with ethylenediamine lPtAX 2-en-PtAX2] (A = ~H 2 , ~H 4 , CO; X = Cl, Br) (6, 20]: the presence of a broad v(NH) band having a fine structure at 326o-3095 cm- 1, as well as a 5(NH2) band at 1590-1555 cm- 1• Second, the absence of bands for the stretching vibrations of
301
s
\
-
I (PI (NIIs)zCI}z'L' )Cit
20,2/20,1 36,6/30,9
21,4/20,5 36,6/36,8
55,2/55,6 44,0/~4.3
53,6/53,9 54.9/55,2 44,3/45,1 55,3/55,0
51i,8/5M 41,!1/44.9
I (Pt(NH,)zCI}zU]Cla
I 11'1 (NH,)2Br}zL 3 )Brz
I {Pt(Nlb)zNOa)zL')Cla
I (Pt(NH,)aCI}zV)Clz·llzO I (Pt(NH 1)tBr}zL2 )Bra
I (Pt(Nih)zNOalzLZ )Clz
I (l't (NII 3 )2Cl}zL 1 )Clz·HaO
[ (Pt(NH,)zBrhl.t)Bra·HaO
3.0/3,4 3,0/3,5 2,3/2,8
6,6/6,8 5,4/5,2 4,4/4, t
12,0/12, t 10,0/9.7
15,4/15,8
1.9/2,8
5,4/5,6
3,2/3,7
3,5/3,6
2,5/3,0
3,5/3,7
3,5/3,5
2,8/3,1
2,8/3,1
3,8/
3,7/3,9
9,5/9,7
I
II
7,4/6,8
8,7/8,3
6,9/6,8
8,4/8,6
9,5/9.1
10.0/9,8
8,8/8.1
10.1/
10,1/10,1
c
11,6/11,9
14,7/15,5
9,1/9,6
11,8/12,0
I
7.
ll '
256
217
199
225
218
181
241
229
213
192
230
-
252
c-1·cm2·mole- 1
*Mean values of the results of the analysis and the conductivity measurements for 4-S experiments are presented. The variability of the values does not exceed ±0.57..
9,3/10.0
10,0/9,8
35,9/36,3
20,7/20,2
17,5/17,7
-
48,7/49,4
I {Pt(Nib)zNOa}zL') (NO,)z
9,9/9,4
11.4/
11,4/11,7
15,0/15,2
I N
Content (found/calculated),
9,0/9.6
52,1/52,9
I (Pl(Nib) aNOz) zL' )Cia
36,5/35,8
19.4/
19,2/19,8
43.4/43,H
I Hal
I {Pt(Mh)zBr}zL')Bra . ..1
(after gel chromatography)
54,2/54,5
l'l
I {Pl(NH,)sCI}zL')Ch
>
Compound
TABLE 1. Results of the Elemental Analysis of Complexes and Values of the Molar Conductivity {J.l) of Their Aqueous Solutions•
J
TABLE 2. Values of R 1 for the Binuclear Complexes of Pt(II) with Polymethylenediamines of the Type trans- [Pt(NH3hX- LPt(NH3hX]X2 Rt L
X
y
system I
L' L' L' L' 13 Ll L3 12 1' 12 L' L'
Cl Br NOz NOz
Cl Br
NOz
Cl Br
NOz
Cl Br
Cl Br Cl N03
Cl Br Cl Cl Br Cl Cl Br
0,29-0.31
-
0,22-0.24 0.20-0.22 0,24-0,26
I
system 2
-
0.42-0.44
-
-
-
0,31-0,33
-
0,32-0,34
-
0,27-0,29
0,18-0.20 0,22-0.24 0.19-0.21 0.28-0.30
-
-
uncoordinated NH2 groups in the polymethylenediamines [v4 ,s{NH) at 3360-3330 and vs(NH) at 3280-3250 cm- 1) attests to the participation of both amino groups in the bonding with the platinum atom. Third, the fact that the spectra of the complexes do not contain a band for the skeletal deformation vibrations which are characteristic of a chelating diamine at 47Q-460 cm-1 [5} allows us to rule out this type of bonding of the ligands to the central atom. These conclusions are consistent with the hypothesis of a binuclear structure for the complexes with a bridging molecule of the polymethylenediamine. The far-infrared spectra of samples in the form of polyethylene tablets were recorded on an Hitachi FIS-3 spectrometer, and the spectra of samples in the form of mulls in liquid petrolatum were recorded in the near-infrared region on a Specord IR 75 spectrometer. The individuality of the complexes isolated was proved with the use of thin-layer chromatography on Silufol UV-254 plates in the following systems: 1) propanol (80 ml) + isobutanol (40 ml) +water (78 ml) +acetic acid (30 ml) +ammonium acetate (1.8 g); 2) ethanol (50 ml) +acetone (40 ml) +water (10 ml) +acetic acid (10 ml) +a 257o solution of ammonia (5 ml). The chromatograms were developed in iodine vapor and by a 0.17o solution of ninhydrin in acetone. Only the spots of the respective complexes were detected in iodine vapor, and ninhydrin imparted a yellow color to the free ligands. The investigation carried out demonstrated the absence of spots corresponding to the original platinum(II) complexes (Rf = 0.68-0.70) or the free ligands studied (R 1 = 0.24-{).27) on the chromatograms under the conditions of the present experiment, which attests to their absence in the compounds isolated. The spots on the chromatographs which became brightly colored in iodine vapor (R 1 = 0.19-0.44) (Table 2) were assigned by us to binuclear complexes of platinum(ll) with bridging polymethylenediamine molecules. At the same time, the presence of a weakly colored spot which hardly moved away from the starting line (R 1 = 0.03-0.07) in all cases points out the presence of an impurity of other Pt(ll) complexes along with the main substance in the reaction products. This impurity may consist of Pt(II) complexes of the triammine and tetraammine types with monodentate coordination of the ligand [21 ], as is evidenced by the presence of spots with R1 = 0.03-0.07 on the chromatograms of the products of the reactions of trans-diacidodiammines of Pt(ll) with the diamines under investigation carried out with Pt:L mole ratios equal to 1:1.and 1:2. Purification of the binuclear complexes for the purpose of removing the impurities by repeated recrystallization and their precipitation in the form of sparingly soluble compounds with tetraphenylborate and chloroplatinite anions still did not make it possible to obtain chromatographically pure products. The isolation of a chromatographically pure binuclear complex with a bridging molecule of 1,6-diaminohexane was accomplished with the aid of gel chromatography. A solution of the complex in 0.1 M LiCl (the volume of the sample was 10 ml) was introduced into a column with the dextran gel Sephadex G-10 (Vcol = 285 ml), and it was eluted by a 0.1 M solution of LiCl. The elution rate was equal to -30 ml/h. The eluate emerging from the column was analyzed fraction-by-fraction by a spectrophotometric method and by TLC on Silufol UV-254 plates in system 1. The fractfons conlairiing the binuclear bridged complex were collected on the basis of the data obtained. They were evaporated to 2-3 ml, and then the complex precipitated together with lithium chloride from the concentrated solution. The LiCl was removed by dissolving it in 5o-60 ml of ethanol, and the remaining complex was filtered out and thoroughly washed with ethanol. The yield was equal to 15-2Q7o. According to the results of the elemental analysis (Table 1), the compound thus isolated corresponds to the binuclear bridged complex with the formula trans-[Pt(NH 3hCl-NH2-(CH2)cNH2-Pt(NH 3)2Cl]C1 2 • Thin-layer chromatography revealed the presence of only one spot with R1 = 0.29-0.31, which attested to the individuality of the compound isolated. Its IR spectrum in the 4000-Ioo-cm- 1 region is completely identical to the spectrum of the product obtained according to reaction (1), and this fact together with the results of the elemental analysis makes it possible to conclude that the product contains
303
TABLE 3. Acid Dissociation Constants of Binuclear Diaquo Ions
I c-~03,
Ion
1.2 2.0 3.4
trans-[Pt(NH3hHzcrNH 2-(CH 2)J-NH2Pt(NH3)zH20]4+
I I
2.0 3.0 5.0
K,·!O'
K,·IO'
2.94 1.99 2,67
2.65 2,21 2,39
Kt=2.5±0,5
K2=2,4±0,3
2.18 3.23 3,09
5,95 4.68 7,78
R'.=2,8±0,6
.K;=6,1±1,6
only an insignificant quantity of impurities, which do not have any influence on the spectroscopic characteristics of the complex. In order to study the influence of the length of the bridging polymethylenediamine molecule on the properties of the binuclear complexes, we studied the acid properties of the diaquo ions of the type trans-[Pt(NH3) 2H 20-L-Pt(NH3) 2 H2or+, where L = L 1, L 4 , by means of potentiometric titrations at 25"C and an ionic strength of the solution equal to 0.3 (KN03) in the concentration range from 1·10-3 to 5-10-3 M. The titrations were carried out by 0.05-Q.l M KOH solutions in a stream of purified nitrogen with the use of a glass electrode an a pH-121 pH-meter. The solutions containing the diaquo ions were obtained· according to reaction (2) with the use of the method of successive dilutions. The investigations showed that these compounds are titrated by potassium hydroxide as weak dibasic acids (the consumption of potassium hydroxide amounted to 2 equivalents per mole of the complex) with close stepwise acid dissociation constants. Their values were calculated according to Speakman's formulas [22] (Table 3). A statistical treatment of the results of the calculations for each titration was carried out with the use of the Student distribution for a confidence coefficient P 0.95 and a sampling size m 16; the random error in the mean values of the constants did not exceed ±0.08 (37o). The error in the determination of the final values of the constants was estimated on the basis of their spread of variation between individual titrations. In contrast to the constants determined for the mononuclear cis- and trans-diaquo ions [Pt(NH:J)2(H20)z)2+ [23], the stepwise acid dissociation constants of the binuclear aquo ions are close to one another (the difference between them does not exceed an order of magnitude), pointing out the independent character of the titration of the water molecules. The value of the first acid dissociation constant K 1 of the binuclear aquo ions practically coincides with the acid dissociation constant of [Pt(NH 3) 3H 20f+, which is equal to 2.5·10-6 [24), attesting to the absence of a specific influence of the trans placement of the bridging diamine on the ability of the water molecules to undergo acid dissociation. At the same time, the closeness of the values of K 1 and K 2 for the aquo complexes of Pt(II) with U and L 4 shows that the length of the carbon chain has practically no influence on the acid properties of water molecules which are distant from one another.
=
=
LITERATURE CITED
l. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18.
304
Yu. N. Kukushkin, The Chemistry of Coordination Compounds [in Russian], Vysshaya Shkola (1985). 1.·1. Chemyaev, Izv. Inst. Platiny, No.5, 102 (1927). A. D. Gel'man, Dokl. Akad. Nauk SSSR, 38, No. 8, 272 (1943). A. D. Gel'man and E. A. Meilakh, Dokl. Akad. Nauk SSSR, 51, No. 3, 203 (1946). P. C. Kong and T. Theophanides, Canad. J. Chern., 45, No. 24, 3193 (1967). T. Theophanides and P. C. Kong, Canad. J. Chern., 48, No.7, 1084 (1970). V. V. Vlasov, S. A. Kazakov, and V. G. Misovets, Dokl. Akad. Nauk SSSR, 266, No. 4, 866 (1982). V. V. Vlasov and S. A. Kazakdv, Bioorg. Khim., 9, No. 4, 530 (1983). A. I. Stetsenko, K. I. Yakovlev, and A. L. VaJs, Koord. Khim .• S, No. 8, 1229 (1979). P. C. Kong and F. D. Rochon, Chern. Commun., No. 15, 599 (1975). A. I. Stetsenko and E. S. Dmitrieva, Koord. Khim., 3, No. 8, 1240 (1977). A. I. Stetsenko, E. S. Dmitrieva, and K. I. Yakovlev, J. Clin. Hematol. Oncol., No. 2, 522 (1977). B. Lippert, Inorg. Chim. Acta, 46, No. 1, Lll (1980). H. Sch6ellhom, U. Thewalt, and B. Lippert, Inorg. Chim. Acta, 93, No. l, 19 (1984). B. Lippert, D. Neugebauer, and C. Raudaschl. Inorg. Chim. Acta, 78, No. 4, 161 (1983). I. I. Chemyaev (editor), Synthesis of Complex Compounds of Platinum Metals [in Russian), Nauka, Moscow (1964). A. Finch, P. N. Gates, K. Radcliffe, F. Dixon, and F. F. Bentley, Chemical Applications of Far Infrared Spectroscopy, Academic Press, New York (1970) [Russian translation: Mir, Moscow (1973)]. M. A. Sarukhanov, M. Sh. Mridkha, Yu. Ya. Karitonov, et al., Koord. Khim .• 7, No. 6, 934 (1981).
M.A. Sart>khanov, M. Sh. ~ridkha, Yu. Ya. Karitonov, et al., Zh. Neorg. Khim., 28, No.8, 2044 (1983). P. Kong and T. Theophamdes, Canad. J. Spectrosc., 14, No. 4, 3 (1969). . A. 1. Stetsenko, G. M. Alekseeva, and K. I. Yakovlev, Koord. Khim., 11, No.8, 1116 (1985). A. Albert and E. Serjeant, Ionization Constants of Acids and Bases, Wiley, New York (1962) [Russian translation: Khimiya. Moscow (1964)]. A. A. Grinberg, Introduction to the Chemistry of Complex Compounds [in Russian], Khimiya, Moscow-Leningrad
c.
(1966). A. 1. Stetsenko and S. A. Pechenyuk, Zh. Obshch. Khim., 45, No. 5, 968 (1975).
305
CT.EAEHRO
.A.u.,. HIWBJIEB n. n.,
POiRIWBA H. ):(., ··.
UOPAPEBA n~r., RA3AROB C. A.
:&ll1l)l;EPHhiE KOMHJIEKCLI Pt (II) C .MOCTIIROBbiMII . MOJIEKYJIAMJI HOJlliMETIIJIEII)l;UAMIIHOB Ilpn: 'lCCKHMII
B3RJIMO,IJ.aiicTBHll
B .BOJWOH cp~/J;e mpaHc-{Pt(NH 3hX 2] C a.ziiiTaTn3-6) Upli MOJihHOM OTBOmemm
UOJHIMeTnJieH,IJ.HRllllHa~{;l{ (n =
= 2 ; :t BhlP;e.JieHhl 6nH.u.epBue KOMn.rreKchi c MOCTHK()BLIMn Mo.rreRy.rrntaap;oB . mna. mpanc-!Pt(NH 3 } 2 X-L-Pt(NH 3 } 2 X}X 2 , r;w X= = CI, Hr, N0 2.• HR cneRT.pocRolllPieCRII ,ll,(nta3ana MocnHWll\aH Roop;:mE:a-
Pt .: L JIRMH
IJ;li.H .J{l:la:l,iliHOB.. .fiOTeHI\HOMe'fpir'!eCRHM MeTO,ll,OM R:ric.rroTnoii .u.ncco:u,nall,IHI p:naKBOllOHOB: K 1 (2,5
onpe,i:ICJJef!¥
+ 0 ,.5) .10-6, K
=
KOBCTaHThl
+
= (2,4 +0,3)·10-7 (AJIH • n = 6) II K 1 = (2,8.+0,6)·10-, K 2 = (6,1 + 1,6)~ · ·10-7 (;n;JJJl n = 3). llx aBan:Ha y.RaausaeT na Be3anncn~mii: xapaRTep TJIT2
poBaBl:IH MOJieKyJI BO,IJ.U B ROMTIJieR.caX •n npaKTH'lecKOe OTC)'TCTBI!e BJlllHc lfiDI p;mutm yrJiepo;n;Bon .qellll 'n:a HHCJIOTHhle cBoiicTna KOHIJ,eBhlX ~H)neKy.rr BO;!J;hl.
o6~e:H K,l],aJIR ;!Ib)J,OM U OTqlliJibTpOBhiBaJill: OT He3Ha'InTe.'lbHOI'0 ROJI;H'leCTBa nenpopearnpo~aBinero mpaw-[Pt(NH 3 )zCI 2l; "d~~~~~~~~;~~~:1i~~.
..· .·.• l'~~; ~Q/Ii~It ll~'~ f;•'ll':~~~' ··..
upoonaM;q:ar,r~. (}~asm~N:aamiCt. .. Q.ffl!AeP~ ·
········"=-~~~~~~:t~~~;:::~~::·:: ;·#iptilJ:t&-fi;~t.(~Jf.$,)~Gl~~~P:t~~H3)2 CHC12+4AgN0 3
+ 2H~O-+
.· ~.mji~tttt4Etf;N~ 3)~ft'20:':'-L~Pt(~H 3)iH~OJ(N0~)4 r+ 4A€tCl,
(2)
.~·~ mpi'LJC~,;[Pt{Nlf3)~H~0.,. L~Pt(NHa}2HiJJ{NO 3) 4 + 4kHr -+ · ~ 4m:pauc-'fftf&;Ha)2'Bri_:,_,L""'-:Pt(NHa)2BrlHr2 +4KNOa..
.· : ~· :0~ '!i~f(lc'l"JI e'0e.rt:U~Htrf! I I
(3) .
5 MJI liOAM, 'uo6aBJIJIJIR ri:Pu K()MHaTHOil· Te~[IIepa..;, 3are~t · oTlf)n.n::&'l'po:SMBa;rrn ·. ocaum{ AgCl.· H
pacTnopeiiHOI'O B
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, ·. ... ·::·.~~~ ~~)~~1r~~;~:~::~;;;~;~~!Jprt~~~~z!;:=~1II '~::JI::!i~6:~L~ oT!f>:rtJ:ti>1'po,a'ima;;ui·, · cywmm . 0 ~~~t\}:~~(ll~~~t~, ~Mo6t~~~~f>IM~ ::liO•'I~KY~~aMII. :no~'In~ ' "!:~::H:2;:~.~ B~~~~h~ pn . . . I>. .··.. ·.
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.. ;·.
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55,3/55,0
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.
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36,6/36,8
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[ {Pt(NHa)zl1r}zV}Br~
20,2/20,1
5'~.9/55,2
[ {Pt(NI-ls)zClhL~]Gh·HzO
..
53,6/53,9
.. [ {Pt(NH.a}aNOa.hVJGl~ 10,0/9,8
·. 35,9/36,3
14,0/44,3
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3
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55,2/55,6
.
48,7/49;4
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.-
9;0/9,6·
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z?l} aL ]Cl:
36;5/3!i,8
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19;2/19;8
43,1/43;6
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;
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10,0/9,7
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,I(orrOJIHHTeJihHhDI ;J.OKa3aTeJinCTBOM TaKOI'O CTpOeHnR BhlgeneHHhlX .KOMIIJieKCOB cayaur:r namr'Ille B nx gnnHHOBO.iiHOBhiX UR CIIeKTpax OAIIHOTIHhlX CIIHI'.ileTHbiX IIO.ITOC IIOrJIOID,eHIIR, COOTBeTCTByiOIIJ,ll.X: BaJI8HTHhl!vf. KOneoaHIIRM CBR31I Pt-X B o6.rracm 348-337 c.M-1 AJIR v(Pt-Cl), 251-232 c~C 1 ,IJ;JIJI v(Pt-Br) [17] II 330-323cM-1 ;J.JIR v(Pt--N0 2 ) [18, 19]. l:fnreprrpeTaiJ.liR I1R CII8KTpOB B:&JAe.ITeHH.hlX coe,IJ;nHennn H8CKO.ilbKO aaTpy,Il;HeHa, TaR KaK B IIX COCTaB BXO,Il;RT ~fO.ITe.KyJihl a).Hflla.Ka, IHfeiQID,He CBOH COOCTB8HHhl8 KOJieoaiDIR v(NH) li 8(NH 2 ) B OO.'IaCTRX 3275..,.--3'100 II 1700__: 1500 C).C 1 coorneTCTBeHHO. 0,IJ;na:Ko II3J>n:renne HR crrelnpoB·cnnTesnpoBaHrr:&IX KO:MIIJieRcon nee me no3no:nv:ro c,IJ;eJian.. PHA saKJIIOTienrrii. Bo-nepnhlx, xapaKTep norJiom,emui B · o6Jiacnrx BaneHTHI>rx II ;:~.eq,op.MaiJ.nOHHLix KoJie6amrH: aMnHorpynn:r,t anaJionrqen Ha6Jiro,IJ;ae.Mm.ry B HR cneKTpax nanecTHhlX 6nn;:~,ep RhlX KOMII.'IeKCOB II.'IaTIIHhl c 3TII.'IeH;:~,naMIIHOM [PtAX 2 - En- PtAX 2 ] (1}. C 2 H:p C 2 H 4 , CO; X Cl, Br) [6, 20]: Ha.'IIITine miipoKoll: IIOJIOCI>I v(NH). IIMe:rom,eii TOHKyro CTPYKTYPY, n o6Jiac:rn 3260-3095 cM- 1 , a TaKme rroJIOChl 6(NH 2 ) rrpR 1590-1555 cM- 1 • Bo-BTOphrx, orcyTCTBIIe rro.'Ioc Ba.'IeHTHhiX KOJie6aHnii HeKoop;:~.nnrrponaHHhlX NH:crpynrr-rro.aii~IeTnJieH;J:IraMrrnoB (vas(NH} 3360-3330 II V 8 (NH) 3280-3250 C).-C1 ) CBII;J.eT8.'IhCTByeT 00 yTiaCTIIU B CBJI3ll c n.rraTUHOll ooenx a.Mnnorpyrrrr. B-TpeThllX, OTCYTCTBlle B CII8I\Tpax KO~fiiJieK COB IIO.iiOChl CK8JI8THhlX ;:1.8c:~a·~o:.ru~et.:.cn?TX cOeJ\Iirieauii' ~teTa:i~os liJJaTI.tnosoii rpy.ririhl l :rio A pe,:t. qep~ . 1ut~~~Il:f!: ;i\l,: l{ayf{a, 1~.6~> 339 c. ; _ . _.. _ . 11: t!Jun"A.:,_(eiim-q·fl·i Pftvn.tt~licn]~}t:A;\ ~lfpuoci4 M~JIL; Xapumo1f,oe10. /l.u &p.
,
·
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1/KoopA. xnMilll. 198L
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