Polyhedron 23 (2004) 955961 www.elsevier.

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11

B NMR study on the interaction of boric acid with Azomethine H

Hidenobu Matsuo a, Yoshinobu Miyazaki b, Hiroyuki Takemura a, Shiro Matsuoka a, Hirofumi Sakashita c, Kazuhisa Yoshimura a,*
a b

Department of Chemistry, Faculty of Sciences, Kyushu University, Ropponmatsu, Chuo-ku, Fukuoka 810-8560, Japan Department of Chemistry, Fukuoka University of Education, Akamabunkyo-machi, Munakata, Fukuoka 811-4192, Japan c The Center of Advanced Instrumental Analysis, Kyushu University, Kasuga, Fukuoka 816-8580, Japan Received 8 October 2003; accepted 2 December 2003

Abstract
11 B NMR spectroscopy provided direct evidence that boric acid reacts with Azomethine H to form a 1:1 bischelate complex. A new peak with a )17.9 ppm chemical shift is due to the chelate complex containing tetrahedral boron. It has been quantitatively conrmed that the reaction includes two chemical equilibria; one is related to the ligand formation and the other to the complex formation. The formation constant for the ligand is small, less than 10, whereas that for the complex is relatively large, greater than 105 . Azomethine H is hydrolyzed in aqueous solution because of its low stability, and the ligand formation is responsible for the nature of its complexation with boric acid. 2004 Elsevier Ltd. All rights reserved.

Keywords: Borate complex; Azomethine H; Boric acid; Complexation;

11

B NMR

1. Introduction A large number of spectrophotometric studies have focused on the development of methods which enable one to determine the concentration of boric acid in an aqueous solution under moderate conditions. The Azomethine H method, proposed by Capelle in 1964 [1], has been employed for the boron analyses of natural and waste waters, soils and plants [210]. Azomethine H (8hydroxy-1-(salicylideneamino)-3,6-naphthalenedisulfonic acid, Fig. 1) is a Schi base of salicylaldehyde and Hacid (1-amino-8-naphthol-3,6-disulfonic acid), and its solution exhibits an absorption maximum at 412 nm in the presence of boric acid. A number of studies have been performed for optimization of conditions for boron determination using Azomethine H as a coloring agent. For this purpose, it is very important to understand well the interaction between boric acid and Azomethine H. It has been pointed
Corresponding author. Tel.: +81-92-726-4743; fax: +81-92-7264842. E-mail address: kazz@chem.rc.kyushu-u.ac.jp (K. Yoshimura). 0277-5387/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2003.12.016
*

out in some papers that Azomethine H reacts with boric acid to form chelate complexes in solution, and then the complexes exhibit an absorption maximum in the visible region [46]. Some possible complexes are shown in Fig. 2, i.e., a 1:1 monochelate complex of trigonal boric acid (I), a 1:1 bischelate complex with tetrahedral boron (II), a 1:1 monochelate complex with tetrahedral boron (III), and its corresponding 1:2 complex (IV) [411]. On the contrary, Harp has suggested that the absorption maximum is due only to the Azomethine H species [7]. However, direct evidence regarding the coloring processes and the structure of the borate complex has not been provided until now. 11 B NMR spectroscopy is an excellent tool for studying the reaction of boric acid/borate with chelating ligands. In our previous studies, the nature of the interaction between boric acid/borate and boron-selective adsorbents such as crosslinked dextran gels, chelating resins with functional groups of N-methylglucamine and chromotropic acid-presorbed resin had been elucidated [1217]. In this study, characteristics of the complexation of boric acid with Azomethine H will be discussed using the 11 B NMR method.

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SO3CH N OH HO SO3-

2.2. NMR measurements B NMR spectra were recorded on a JEOL JNMGSX 500 spectrometer (the Center of Advanced Instrumental Analysis, Kyushu University) at a resonance frequency of 160.0 MHz with a 10 mm multinuclear probe at 25 1 C. The sample solution (I 0:10 mol dm3 , KCl) containing known amounts of boric acid/ borate and ligand was prepared, and the pH was adjusted with a small amount of buer solution. After being allowed to stand for about 1 day, the solution was used for the NMR measurement. The standard NMR parameters were as follows: the ip angle was ca. 90 (36 ls), the pulse repetition time was 1 s, and the spectral width was 31 kHz. The chemical shifts were determined with reference to a 0.1 mol dm3 boric acid solution as an external standard. On this scale the signal of BF3 OEt2 , the generally accepted reference, came at )19.4 ppm.
11

Fig. 1. Chemical structure of Azomethine H.

SO3N O B HO SO3(I) SO3 N O HO BOH O SO3O3S ( IV ) O
-

SO3N O B O SO3( II ) O3S N O B/ HO

5-

3. Results and discussion 3.1. 11 B NMR spectra of the boric acidAzomethine H system The values of the 11 B NMR chemical shifts allow us to estimate the structures of the boron species [1822]. If free boric acid of a trigonal planer structure is used as an external reference, the signal due to free borate anion having the tetrahedral structure appears around )17.7 ppm. When boric acid reacts with chelating ligands to form a complex with a six-membered ring structure, the 1:1 monochelate complexation shows a signal around )18.3 ppm, and further 1:2 bischelate complexation adds a new peak around )18.9 ppm. The 11 B NMR spectra of boric acid in the presence of Azomethine H in weakly acidic regions varied with a change in the total concentration ratio of Azomethine H to boron. Fig. 3 shows that a new peak due to the complex appears in addition to that of free boric acid and that the chemical shift value for the complex is )17.9 ppm. Moreover, it was apparent that there was only one complex in this system, because no more peaks were observed even at higher Azomethine H concentrations. The relative peak areas of the 11 B NMR spectra are directly proportional to the relative concentration of the respective boron species [1921]. Fig. 3 shows that the concentration of the complex depends on the relative concentration ratio of ligand to boric acid. On the assumption that the complexation is a simple reaction expressed by Eq. (1), we calculated the concentration quotients, Q, using Eq. (2) and the concentrations estimated by 11 B NMR measurements Azomethine H BOH3
complex 1

2 2

( III )

Fig. 2. Possible complexes of boric acid with Azomethine H.

2. Experimental 2.1. Reagents All chemicals except Azomethine H and H-acid were of analytical reagent grade. All solutions of chelating agents were freshly prepared. Azomethine H (reagent grade), purchased from Dojindo (Japan) as the disodium salt, was used without further purication. A 20.0 mmol dm3 Azomethine H solution was prepared by dissolving 0.467 g of the reagent in 50 cm3 of a 10 mmol dm3 ascorbic acid solution. A 20.0 mmol dm3 salicylaldehyde solution was prepared by dissolving 0.122 g of salicylaldehyde in 50 cm3 water with the addition of a small amount of KOH solution. The H-acid, 1-amino-8naphthol-3,6-disulfonic acid, was received as a reagent grade monosodium salt (86.1%, Tokyo Kasei, Japan) and was used without further purication. A 10.0 mmol dm3 H-acid solution was prepared by dissolving 0.449 g of H-acid in 100 cm3 water with the addition of a small amount of KOH solution. Deionized water prepared with a Milli-Q SP system (Millipore, USA) was used throughout. The pH of the solution was adjusted with a 0.1 mol dm3 acetate buer, phosphate buer, HEPES buer, or KOH solution and was measured with a Horiba pH meter, Model F-22. The ionic strength was kept at 0.10 mol dm3 with potassium chloride.

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Fig. 3. 11 B NMR spectra for the solution containing 10.0 mmol dm3 Azomethine H (pH 6.5). ((a): 5.00 mmol dm3 , (b): 10.0 mmol dm3 boric acid/borate).

complex : Azomethine HBOH3

Fig. 4. 11 B NMR spectrum for the 10.0 mmol dm3 boric acid/borate solutions containing H-acid or salicylaldehyde. ((a): 10.0 mmol dm3 H-acid, pH 6.5; (b): 50.0 mmol dm3 salicylaldehyde, pH 8.5).

The calculated Q had signicantly dierent values when the concentration ratios of boric acid to the total Azomethine H were dierent, suggesting that such a simple equation could not explain the complexation reaction (Table 1), and therefore some other reactions may be involved in this system. 3.2.
11

salicylaldehyde or H-acid is negligible in the weakly acidic region. 11 B NMR spectra for weakly basic solutions containing ascorbic acid, Azomethine H and boric acid/borate also gave new peaks due to the interaction between borate and ascorbic acid [23], but these peaks were not recorded under weakly acidic conditions. 3.3. The structure of the boric acidAzomethine H complex As mentioned above, the interaction of boric acid with Azomethine H gave only one complex with a new peak in the 11 B NMR spectrum. The chemical shift value for the complex was )17.9 ppm, indicating that the structure of the chelate complex consisted of tetrahedral boron, not of trigonal boron such as (I) in Fig. 2. The results under the condition of CB =CL 1:0 in Table 1 indicate that the boric acidAzomethine H complex should not be a 1:2 chelate such as in Fig. 2 (IV) but a 1:1 chelate complex, because the equilibrium concentrations of the complex exceeded more than half of the

B NMR spectra of the starting material systems

Azomethine H is a Schi base and hydrolyzes to yield salicylaldehyde and an H-acid. The 11 B NMR spectra for boric acid solutions with the starting materials of Azomethine H are shown in Fig. 4. Both spectra showed not only the peak of free boric acid/borate but also those of complex species with a chemical shift around )17.7 ppm. In the salicylaldehyde system, the peak of the complex species was not observed in weakly acidic solutions. The relative peak areas of chelating boron species were much smaller than that of boric acid Azomethine H, even if the molar ratios of these ligands to boric acid were higher than that for the Azomethine H system. Thus, the interaction of boric acid only with
Table 1 Concentration quotients for the boric acid and Azomethine H system CB :CL a 1.0:1.0 0.5:1.0
a

pH 4.72 6.50 4.72 6.43

[Free B]/mmol dm3 3.8 3.7 0.60 0.65

[complex]/mmol dm3 6.2 6.3 4.4 4.3

log(Q/mol1 dm3 ) 2.5 2.5 3.0 3.0

CL , total concentration of Azomethine H, 10.0 mmol dm3 ; CB , total concentration of boric acid

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total concentrations of the ligand. Moreover, the equilibrium concentrations of the complex were independent of the pH of the solutions in weakly acidic regions if other conditions were the same. The complexation of boric acid under acidic conditions progresses with a nucleophilic attack of the ligand on the empty orbital of boric acid [16]. The 1:1 monochelate complex presented in Fig. 2 (III) is excluded as the boric acidAzomethine H complex, because the complexation equilibrium must be aected by pH, as expressed by Eq. (3).
SO3-

OH SO3N HO B HO O SO3(V) O B OH ( VI ) HO N HO

SO3-

SO3-

Fig. 5. Possible Azomethine Hboric acid complexes having a coordination bond with a nitrogen atom.

N OH HO SO3+ B(OH)3

H2L

2-

B
SO3-

N O HO BOH O + H3O+

SO3-

BL3-

Intramolecular hydrogen bonding may suppress the protonation of the nitrogen atom of Azomethine H. In addition, it has been reported that the chemical shift value of the complex with coordination via the nitrogen atom is similar to those generally observed for the complex having a BO bond [18]. Therefore, the possible structure of the Azomethine Hboric acid complex should be a 1:1 chelate complex having a coordination bond with the nitrogen atom of Azomethine H such as (II) in Fig. 2. As expressed by Eq. (4), such a complexation equilibrium does not involve proton dissociation.
SO3-

Fig. 5 also shows possible structures of the Azomethine Hboric acid monochelate complex having a coordination bond via the nitrogen atom. According to the 11 B NMR spectrum of the H-acid system in Fig. 4, the possibility of the monochelate complex shown in Fig. 5 (V) will be small. Regardless of the presence of 100 mmol dm3 amine derivatives such as 4-aminobenzenesulfonic acid and 6-amino-1,3-naphthalenedisulfonic acid, the solutions containing 10 mmol dm3 boric acid/borate and 50 mmol dm3 salicylaldehyde gave the same spectra as those shown in Fig. 4, indicating that the monochelate complex such as (VI) in Fig. 5 will be unstable. These results suggest that the possible structure is the 1:1 bischelate complex represented by (II) in Fig. 2. If there is a chelate complex with the boron atom having multiple chelate rings, more than one peak is usually observed in the 11 B NMR spectrum. In this system, both of the two 1:1 monochelate complexes illustrated in Fig. 5 may not be very stable and may immediately form the bischelate complex. These are the reasons why the interaction between boric acid and Azomethine H provides only one complex. 3.4. Complexation equilibria of the boric acidAzomethine H system

N OH HO SO3+ B(OH)3

H2

L2-

B
SO3 -

N O HO B O SO3 + 2 H 2O

BL2-

Similar NMR measurements were performed for solutions containing boric acid, salicylaldehyde and Hacid. The 11 B NMR spectra of 5.00 mmol dm3 boric acid and salicylaldehyde solutions to which H-acid had been added at various concentrations at pH 4.94 showed the same peak as that assigned to the complex (Fig. 6). The relative peak area was dependent on the total concentration of H-acid. Because the reaction of boric acid only with salicylaldehyde or H-acid can be negligible as mentioned above, it was conrmed that the reaction between boric acid and Azomethine H involves two chemical equilibria: one is related to the ligand formation (Eq. (5)) and the other to the complex formation (Eq. (4)).

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Fig. 7. Eect of increasing concentration of H-acid on the equilibrium concentration of the complex (9.60 mmol dm3 salicylaldehyde, 10.0 mmol dm3 boric acid/borate solution at pH 6.67. Standing time: 1 day (+), 1 week ()). Solid line: calculated concentration of the complex using the KfLC value.

Fig. 6. 11 B NMR spectra for the solution containing 5.00 mmol dm3 boric acid, 5.00 mmol dm3 salicylaldehyde and various concentration of H-acid (pH 4.94). ((a) 5.00 mmol dm3 ; (b) 2.00 mmol dm3 ; (c) 1.00 mmol dm3 H-acid).

SO3-

O O
H

H2N +
H

turns brown if the solution is allowed to stand for a long period [2,4,68]. The sample solutions containing boric acid, salicylaldehyde and H-acid became apparently browner with the increase in the concentration of uncomplexed H-acid. Fig. 7 shows variations in the equilibrium concentrations of the complex with time at dierent concentrations of H-acid. Although the changes in sample color resulted in a higher reagent blank for the boron determination, a decrease in the equilibrium concentrations of the complex was not observed. These results indicate that the decomposition of the starting materials of Azomethine H is involved in the reaction. Fig. 8 shows that the complexation equilibrium is independent on the pH of the solution at least under weakly acidic conditions. Both starting materials of

O SO3-

HS

HA2-

5
SO3-

N OH HO SO3+ H2O

H2L2-

When dissolved in aqueous solution, almost all of the Azomethine H is hydrolyzed to yield its starting materials. It is well-known that H-acid is unstable in aqueous solution and that the color of Azomethine H solution

Fig. 8. pH dependence of the equilibrium concentration of the complex (10.0 mmol dm3 salicylaldehyde, boric acid/borate, and H-acid solution. Standing time: 1 day (+), 1 week ()). Solid line: calculated concentration of the complex using the KfLC value.

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Azomethine H contain functional groups relating to acid dissociation reactions expressed as follows:
- H+ O O H + H+ OO

KfC

BL2 : H2 L2 B

HS
SO3+

SSO3H2N H O H2N
-

SO3-

H 3N O

- H+ + H+

- H+ + H+

However, the KfL value was too small and could not be experimentally obtained, because the mixed solution of the starting materials did not give any measurable absorption bands due to Azomethine H in the UV and visible regions. Therefore, the overall equilibrium constant, KfLC , dened by Eq. (10) and the product of KfL and KfC , was estimated KfLC KfL KfC BL2 : HSHA2 B 10

O SO3-

H SO3SO3-

H2A-

HA2-

A3-

Because the Schi base formation from primary amine and aldehyde proceeds by nucleophilic attack of free amine on the aldehyde [3,24,25], salicylaldehyde condenses with HA2 or A3 of the H-acid species to form Azomethine H. The acid dissociation constant of salicylaldehyde was determined spectrophotometrically to be 108:14 (I 0:1 mol dm3 , KCl, 25 C), and therefore HS in Eq. (6) is predominant in acidic solution. In the case of H-acid, acid dissociation constants for Eq. (7) were not available from the literature, but the predominant species is supposed to be HA2 in the weakly acidic region because it can form intramolecular hydrogen bonding. It was concluded that the reaction includes two chemical equilibria with respect to Eqs. (4) and (5). The equilibrium constants (KfL and KfC ) are dened by Eqs. (8) and (9), respectively. KfL H2 L2 ; HSHA2 8

Eq. (11) may account for the overall reaction in this system HS HA2 B
BL2 3H2 O 11

The mass balance equations for the total concentrations of salicylaldehyde CS , H-acid CA and boric acid CB are then expressed as follows: CS HS BL2 ; CA HA2 BL2 ; CB B BL2 : 12 13 14

The KfLC value could be determined based on the relative intensities of the 11 B NMR signals. Table 2 shows that the KfLC value is constant at 105:910:07 under different conditions. The equilibrium concentrations of the complex calculated using the constant are compared with those observed experimentally as a function of the total Hacid concentration or pH (Figs. 7 and 8). While almost all of the H-acid reacts to form the bischelate complex in

Table 2 Formation constant for complexation of boric acid with salicylaldehyde and H-acid pH 4.24 4.85 4.94 5.00 4.96 CB a /mmol dm3 10.0 CS b /mmol dm3 9.57 CA c /mmol dm3 10.0 10.0 1.00 2.00 3.00 4.00 5.01 10.0 10.0 8.01 10.0 12.0 [Free B]/mmol dm3 2.21 2.15 4.06 3.22 2.53 2.04 1.71 2.05 2.16 3.17 2.33 1.88 [complex]/mmol dm3 7.79 7.85 0.94 1.78 2.47 2.96 3.29 7.95 7.84 6.83 7.67 8.12 log(KfLC /mol2 dm6 ) 5.94 5.99 5.95 5.89 5.86 5.84 5.82 6.06 5.98 5.83 5.87 5.89 5.91 0.07

5.36 6.02 6.67

10.0

9.57

CB , total concentration of boric acid. CS , total concentration of salicylaldehyde. c CA , total concentration of H-acid.
b

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the presence of excessive amounts of boric acid and salicylaldehyde, increased proportions of the H-acid did not produce any new peaks due to other unexpected complexation reactions. The experimental results were on the calculated solid lines. These gures show that the lines reproduce well the experimental results and that the KfLC value can be applicable to any experiments under dierent conditions. Our results, thus obtained, oer some useful information for optimization of the conditions for boron determination. The Azomethine H method can be performed using a mixed solution of the salicylaldehyde and H-acid instead of their condensation product, as suggested by Harp [10] and Staden [7]. By keeping the H-acid concentration low enough to form the chelate complex, the reagent blank for the boron determination due to the decomposition of H-acid can be reduced as much as possible. As mentioned above, the KfL value was too small and could not be experimentally obtained. On the assumption that the molar absorptivities of Azomethine H are similar to those of its boric acid complex (e.g., 103 mol1 dm3 cm1 at 412 nm), the KfL value was roughly calculated. The absorbance of the mixture solution of the starting materials at 103 mol dm3 was almost the same as the sum of the absorbances of their individual solutions and the dierence was less than 0.01. The equilibrium Azomethine H concentration in the mixture solution was estimated to be lower than 105 mol dm3 and the KfL value to be less than 10. Therefore, the KfC value should be greater than 105 . This complexation constant is comparable to those of the most stable 1:2 bischelate complexes (approximately 106 ) [16]. On the contrary, the 1:1 bischelate complex formation constant is much greater than that of the corresponding complex with triethanolamine [18]. Such a large stability is due to the structures of the complex and the ligand. The bischelate complex may be stabilized by the delocalized sp2 character of the ligand. Intramolecular hydrogen bonding allows the conformation of the free ligand to be that shown in Fig. 1, and the structure is suitable for interaction with boric acid to form the complex.

only be due to the free ligand. In this work, the complexation of boric acid with Azomethine H could be quantitatively claried by a 11 B NMR study: the starting materials of Azomethine H (H-acid and salicylaldehyde) yield the 1:1 bischelate complex including BN bonding only in the presence of boric acid.

Acknowledgements This work was partially supported by the Steel Industry Foundation for the Advancement of Environmental Protection Technology.

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4. Conclusion The Azomethine H method is a practical spectrophotometric method for boron analysis applicable under mild conditions. However, the interaction of boric acid with Azomethine H has been unclear for a long time. There are some possible complexes shown in Fig. 2, or a possibility that light absorption in the visible region can