Spectrochimica Acta Part A 58 (2002) 3085 /3092 www.elsevier.

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Infrared spectra of new Re(III) complexes with thiourea derivatives

Dinorah Gambino a, Eduardo Kremer a, Enrique J. Baran b,*
b

Catedra de Qumica Inorganica, Facultad de Qumica, Universidad de la Republica, 1300-Montevideo, Uruguay Centro de Qumica Inorganica (CEQUINOR/CONICET,UNLP), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, C.Correo 962, 1900-La Plata, Argentina Received 5 November 2001; accepted 15 January 2002

Abstract Complexes of the type [ReIIIL6]X3, with L0/thiourea, N -methylthiourea, N -ethylthiourea or N ,N ?-di( methytlthiourea and X 0/Cl( or PF6 , were prepared as suitable precursors for the synthesis of new rhenium complexes potentially useful in nuclear medicine. The infrared (IR) spectra of these complexes were recorded and analyzed and a general vibrational pattern for Re(III) complexes with thiourea derivatives could be established. Approximate assignments for N -allylthiourea and N -ethylthiourea are also proposed for the first time. The synthesis of the new complex [ReIII(N -allylthiourea)6](PF6)3 is also reported, and information about its structural characteristics was obtained comparing its IR spectrum with those of the other complexes of the investigated series. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Re(III) complexes; Thiourea derivatives; Infrared spectroscopy

1. Introduction Radiopharmaceuticals, i.e. drugs containing a radionuclide, are increasingly used for diagnostic and therapeutic purposes [1]. They are usually small organic or inorganic compounds with definite composition or macromolecules such as monoclonal antibodies or antibody fragments that are not stoichiometrically labeled with a radionuclide.

* Corresponding author. Tel.: '/54-221-4259485; fax: '/54221-4259485 E-mail address: baran@quimica.unlp.edu.ar (E.J. Baran).

Due to the extensive use of the g-emitter 99mTc in diagnostic nuclear medicine [1 /5] and the potential usefulness of 186Re and 188Re for radiotherapeutic purposes [6,7], the chemistry of technetium and rhenium has become a very active field of research [1,8/10]. Ligand substitution onto suitable precursors is an important route of synthesis of technetium and rhenium complexes. As thiourea is a poor ligand, its easy substitution under mild conditions turned [TcIII(thiourea)6]Cl3 into a useful precursor to other Tc(III) compounds in solution [11]. So [99mTc(thiourea)6]3' was tried as starting material for the synthesis of 99mTc complexes in low concentrations, suitable for radiopharmacy [12].

1386-1425/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved. PII: S 1 3 8 6 - 1 4 2 5 ( 0 2 ) 0 0 1 0 6 - 3

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As a part of a research project devoted to the synthesis and characterization of rhenium complexes potentially useful as precursors for the synthesis of radiopharmaceuticals, we synthesized a series of new Re(III) complexes with thiourea and thiourea derivatives and investigated their general physicochemical properties [13 /15]. Complexes with the general formula [ReIIIL6]3', where L is thiourea (tu), N -methylthiourea (Metu), N ethylthiourea (Ettu), N -allylthiourea (Atu0/N (2propenyl)thiourea) or N ,N ?-dimethylthiourea (Me2tu), were synthesized and characterized by means of different techniques. Ligand formulas are depicted in Table 1. The structures of [Re(tu)6]Cl3 /4H2O, [Re(Metu)6](PF6)3 /H2O, [Re(Ettu)6](PF6)3 and [Re(Me2tu)6](PF6)3 were solved by X-ray diffraction methods [13 /15]. In the framework of this project we have now investigated the vibrational spectra of these complexes in order to identify their most important and characteristic bands and to establish a general vibrational pattern for rhenium and other metal complexes containing thiourea derivatives as ligands. The establishment of this pattern was based on the knowledge of the crystal structures of most of the investigated complexes and it was also applied to the structural study of the new Re(III)/N -allylthiourea complex, whose structure is so far not known. In this paper we also report the synthesis of two salts of this complex.

fluorophosphate salt by keeping the final solution at (/5 8C for 1 h and adding 0.5 ml of a 6M NaPF6 aqueous solution. The oily product was kept at (/5 8C for some weeks and an orange powdered solid could finally be collected. Yield: 35%. The chloride salt was isolated from the synthesis solution by cooling it at (/5 8C during several days. Yield: 12%. Elemental and thermal analyses of the salts agreed with the formulas [Re(Atu)6](PF6)3 /2H2O and [Re(Atu)6]Cl3, respectively. 2.2. Infrared spectroscopy The infrared (IR) spectra (4000 /400 and 400 / 200 cm(1) of the complexes and the free ligands were recorded either as KBr or polyethylene pellets with a Bomen FTIR model M102 instrument. A total of 60 scans were accumulated. Spectral resolution was 9/4 cm (1.

3. Results and discussion 3.1. Structural characteristics of the complexes Structural characteristics of most of the investigated complexes have been previously published [13 /15]. For the new Atu complexes structural data are still missing, as it was impossible to obtain single crystals adequate for diffractometric studies. The most relevant structural information is summarized in Table 2. Average Re /S, C /S, and C /N distances are similar in all complexes and, as expected, they are similar to those reported for the analogous isostructural technetium compounds [16,17]. All
Table 1 Formulas of the thiourea derivatives used as ligands RNH/ C(S)/NHR? R Thiourea (tu) N -methylthiourea (Metu) N -ethylthiourea (Ettu) N -allylthiourea (Atu) N ,N ?-dimethylthiourea (Me2tu) H CH3 CH3 /CH2 CH2 /CH/CH2 CH3 R? H H H H CH3

2. Experimental 2.1. Synthesis of the complexes The investigated complexes [ReIIIL6]X3 /n H2O, where L 0/tu, Metu, Ettu and Me2tu and X 0/Cl ( ( or PF6 , were obtained following the general synthetic procedures previously described [13,14]. The compounds [ReIII(Atu)6]X3 /n H2O were synthesized following an analogous procedure. SnCl2 /2H2O (200 mg, 0.89 mmol) was dissolved in 2N HCl (5.5 ml). A mixture of Atu (1 g, 9 mmol) and NH4ReO4 (100 mg, 0.37 mmol) was added. The orange solution was stirred for 6 h at room temperature and filtered off. The [ReIII (Atu)6]3' complex was isolated as the hexa-

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Table 2 Relevant structural characteristics of the investigated compounds [ReIII(tu)6] Cl3 /4H2O [13] Monoclinic, C 2/c , Z 0/4. ReS6-environment: roughly octahedral. Average bond distances (A): d (Re /S)0/2.421(2); d (C /S) 0/1.746(8); d (C /N)0/1.32(1) Triclinic, P ((/1), Z0/1. ReS6-environment: roughly octahedral. Average bond distances (A): d (Re /S)0/2.432(2); d (C /S) 0/1.749(7); d (C /N)0/1.309(10) Orthorhombic, P 21cn a, Z 0/4. ReS6-environment: roughly octahedral. Average bond distances (A): d (Re /S)0/2.423(4); d(C/S)0/1.74(2); d(C/N)0/1.32(2) Monoclinic, P 21/c , Z 0/4. ReS6-environment: roughly octahedral. Average bond distances (A): d (Re /S)0/2.427(3); d (C /S) 0/1.74(1); d (C /N)0/1.32(2)

[ReIII(Metu)6] (PF6)3 /H2O [15]

[ReIII(Ettu)6](PF6)3 [14]

[ReIII(Me2tu)6] (PF6)3[14]

a Related to the standard space group Pna 21 by the interchange of a and c axes.

complexes show significant departures from the ideal octahedral symmetry. They exhibit longer average C /S distances and shorter average C /N distances than the free ligands. As a result of complexation through the thiocarbonyl sulfur, the C /S bond diminishes its double bond character and the C /N bond increases it. The C /N bonds of the free thiourea derivatives have an evident double bond character. Therefore, N -alkylthioureas can exist in different configurations where the thioamide H atom and the thiocarbonyl bonds are either cis or trans . For the Ettu and Metu complexes the six alkylthiourea ligands have the cis configuration, i.e. the alkyl groups are oriented away from the Re atom. In [Re(Me2tu)6](PF6)3 all the dimethylthiourea ligands have the cis /trans configuration as in the free ligand. 3.2. IR spectra The complexity of the spectra increases from tu to Atu and Me2tu as the number of alkyl groups or the chain length of them increases. Despite the complexity of the spectra, most of the bands could

be tentatively assigned. This assignment was done by comparison with previously reported assignments for the free ligands tu, Metu and Me2tu [18 / 20]. Assignments for the Atu and Ettu ligands were not available in the literature, but Metu and Ettu show very similar spectral patterns. Thus, a tentative assignment of Atu and Ettu bands was performed by comparison with the assignment reported for Metu and taking into account general features of the vibrational behaviour of organic compounds [21 /23]. Results are presented in Table 3 and the recorded spectra are shown in Figs. 1 and 2. Only the relatively strong bands found at 1251 (Atu) and 1263 cm (1 (Ettu) could not be assigned with certainty. A similar band, found at 1259 cm(1, in the spectrum of Metu was also not assigned [19]. Some general conclusions could be derived from the comparative analysis of the spectra and specially in relation to the changes detected after coordination of the mono- and dialkylthioureas to the Re(III) center through their thiocarbonyl sulfur atom. The main changes observed are summarized in Table 4. The ambidentate ligands are potentially capable of interacting with metal centers via its sulfur or nitrogen atoms. There are at least three major stretching vibrations that present strong diagnostic value in relation to the binding mode of these ligands: n(CS), n(CN) and n(NH2) or n (NH). After coordination, a lowering of the frequency of the n (CS) vibration, due to the generation of the Re /S bond, accompanied with an increase of the n(CN) stretching, as a consequence of the simultaneous reinforcement of this bond, should be expected. Both effects were clearly detected in the analysis of the structural data obtained by X-ray diffractometry [13 /15]. However, most of the IR bands of the investigated ligands originate in strongly coupled vibrational modes, and the interpretation of band shifts observed after complexation must be made with great care. The existence of intermolecular hydrogen bonds usually produces broadening and spectral complexity in the bands corresponding to the symmetric and antisymmetric NH stretchings (n(NH2) and/or n (NH)), usually seen as a strong or medium intensity, not completely resolved, group of bands

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Table 3 Assignment of the main infrared (IR) bands of N -allylthiourea and N -ethylthiourea in the spectral range 4000 /400 cm (1 N -allylthiourea Band position 3439 vs 3270 s 3231 s 3179 s 3075 m, 3060 m 3011 m 2967 w 2933 w 2852 w 1867 w 1640 m 1629 vs 1542 vs 1500 s 1435 s 1406 m 1355 m 1316 vs 1251 vs 1137 m 1063 s 998 vs, 929 s 778 s 730 s 658 s 618 m 570 s 447 s Assignment nas(NH2) Overtone d (NH2) n (NH) ns(NH2) nas( /CH2) n (/CH) ns(/CH2) nas(CH2) ns(CH2) Harmonic of p (CH) n (C/C) d (NH2) n (CN), d (NCN), n (CS) nas(CN) d (CH2) d ( /CH) t (CH2), v (CH2) d (NH) r (NH2) n (C?N), ns(CN) p (CH) n (CS) t (NH2) d (CNC) d (SCN) n (C?N) v (NH2) t (CN), p (NH) d (NCN), d (SCN) N -ethylthiourea Band position Assignment

3333 vs 3237 s 3153 vs 2972 s 2927 s 2875 s 2855 s 1636 vs, 1623 vs 1562 s, 1543 vs 1498 m 1469 m 1447 m 1380 m 1347 m 1306 m 1263 s 1127 m 1110 s 1080 w 1031 w 1008 w 891 m 805 vs 740 s 645 s 545 s 492 s 444 m, 425 m

nas(NH2) n (NH) ns(NH2) nas(CH3) nas(CH2) ns(CH3) ns(CH2) d (NH2) n (CN), d (NCN), n (CS) nas(CN) das(CH3) d (CH2) ds(CH3) t (CH2), v (CH2) d (NH) r (NH2) n (C?N), ns(CN) Mainly skeletal vibrations

r (CH3), r (NH2) n (CS) t (NH2) d (CNC) d (SCN) n (C?N) t (CN), p (NH) d (NCN), d (SCN) p (CS)

vs, very strong; s, strong; m, medium; w, weak.

in the 3300 /3000 cm (1 region. This effect is observed in both the free ligands and the investigated Re(III) complexes. Additionally, part of these N/H motions are often masked by the O / H stretching bands of the crystallization water. Additional changes often occur due to modifications of the hydrogen bond networks after complex formation. Despite these considerations, Table 4 shows that in all cases a band displacement of the group of bands associated with the NH stretchings can be observed after coordination. Although the n(CN) stretchings are strongly mixed with other vibrations, the high-energy shift, expected after complexation, is clearly evident from the data presented in Table 4 for some of

the bands mainly associated with this vibrational mode. In most cases, the observed shift is also accompanied with an important intensity diminution. Certainly, the most significant spectral change caused by complex formation is the decrease of the n(CS) stretching frequency. Although this vibration is also strongly coupled with other modes, our assignment of the band with the highest n(CS) character is based on the previously reported normal coordinate analyses for tu, Metu and Me2tu. These studies pointed to a strong band around 700/800 cm (1 as the feature with major PED contribution of this vibrational mode [18 / 20]. All the commented spectral modifications

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Fig. 1. FTIR spectrum of allylthiourea (Atu) between 4000 and 400 cm (1.

between the free ligands and the corresponding Re(III) complexes are consistent with the S-bonding to the metal center, and are supported by the crystallographic studies [13 /15].

On the other hand, although the spectral information for the related technetium complexes remains scarce, some brief comparisons could be made. For [Tc(tu)6]Cl3 /4H2O the n(CS) vibration

Fig. 2. FTIR spectrum of ethylthiourea (Ettu) between 4000 and 400 cm(1.

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Table 4 Summary of the main changes detected in the infrared (IR) spectra of the ligands L, after coordination Main vibration n (NH2) and/or n (NH) Ligand L IR band/cm (1 tu Metu Me2tu Ettu Atu Bands mainly assigned to n (CN) tu Metu Me2tu Ettu Atu tu Metu Me2tu Ettu Atu 3356 s, 3258 s, 3156 s, 3097 s 3350 3305 3333 3439 1473 1560 1560 1562 1542 730 778 725 805 778 s, s, s, s, 3230 s, 3139 s br 3237 s, 3153 s 3231 s, 3179 s [ReL6]X3 [Re(tu)6]X3 [Re(Metu)6]X3 [Re(Me2tu)6]X3 [Re(Ettu)6]X3 [Re(Atu)6]X3 [Re(tu)6]X3 [Re(Metu)6]X3 [Re(Me2tu)6]X3 [Re(Ettu)6]X3 [Re(Atu)6]X3 [Re(tu)6]X3 [Re(Metu)6]X3 [Re(Me2tu)6]X3 [Re(Ettu)6]X3 [Re(Atu)6]X3 IR band/cm(1 3459 s, 3344 s, 3173 s, br; partially masked by H2O vibrations 3348 s, 3318 s, 3282 s 3388 /3299 s 3371 s, 3310 s, 3271 s 3436 s, 3268 s, 3195 s 1512 1578 1606 1575 1581 679 755 715 776 740 w,1099 w s, 1503 s s, 1527 s s, 1509 s m, 1502 m

s,1086 m s, 1503 m s, 1506 s s, 1498 m s, 1500 m

n (CS)

s s m s m

s m m m s

s, strong; m, medium; w, weak; br, broad.

was found at 685 cm (1 [16]; from the other data reported in this paper we assigned the bands located at 1510 and 1100 cm (1 to n(CN) vibrations. As can be seen, these values lie very close to those found for the analogous Re(III) complex (Table 4). A similar coincidence is found in the case of [Tc(Metu)6](PF6)3 /H2O, for which the n (CS) vibration is found to lie at 755 cm (1 [17]. Unfortunately, it was not possible to identify with certainty IR bands related to Re /S vibrations. The identification of this kind of band comparing the low-frequency IR range of the free ligands and their corresponding Re(III) complexes was not totally straightforward since the former present an important number of bands in this region. The very scarce information available for thiourea complexes suggest that IR bands related to M /S vibrations may be expected in the 200 /300 cm(1 range [24 /26]. Therefore, we propose only a tentative assignment for the Re /S vibration in the alkylthiourea complexes as follows: 342 cm (1 for the Me2tu complex, 324 cm (1 for the Atu complex, 326 cm (1 for the Metu complex and 337 cm (1 for the Ettu complex (measured in all cases on the hexafluorophosphate salts).

The assignments proposed for N -allylthiourea and the new [Re(Atu)6](PF6)3 complex are shown in Tables 3 and 5 and the spectrum of the complex is presented in Fig. 3. Interestingly, most of its vibrational frequencies are similar to those of the other investigated Re(III) complexes (cf. also Table 4). These analogies point to similar coordination and structural characteristics. Therefore, it can be assumed that the [Re(Atu)6]3' cation also presents a pseudo-octahedral symmetry with the six Atu ligands bonded to the central Re(III) ion through the thiocarbonyl sulfur atoms. On the other hand, a comparison of the spectra presented in Figs. 1 and 3 shows a clear simplification of the spectral pattern, accompanied with drastic intensity changes, after complex formation. The same behaviour is observed in all the other cases, comparing the spectra of the free ligands with those of the corresponding Re(III) complexes. To conclude, the present study has allowed us to define a characteristic vibrational spectroscopic pattern for Re(III) complexes of thiourea and some of its alkyl derivatives. This knowledge may be useful for the analysis of the spectroscopic behaviour of other coordination compounds holding the N /C(S) /N moiety, including thiocarba-

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Table 5 Assignment of the main infrared (IR) bands of [Re(Atu)6](PF6)3 /2H2O Band (cm (1) 3436 3373 3268 3195 3117 1646 1614 1581 1502 1434 1417 s m s vs vs vs s m s m m Assignment nas(NH2) Overtone (?) n (NH) ns(NH2) nas( /CH2) n (C/C) d (NH2) n (CN), d (NCN), n (CS) nas(CN) d (CH2) d ( /CH) Band (cm (1) 1375 w 1290 m 1244 w 1137 w 993 w 848 s 740 s 620 w 590 w 559 m 480 s Assignment t (CH2), v (CH2) d (NH) ? r (NH2) p (CH) nas(PF3) n (CS) v (NH2) t (CN), p (NH) das(PF3), t (CN), p (NH) d (NCN), d (SCN)

vs, very strong; s, strong; m, medium; w, weak.

Fig. 3. FTIR spectrum of [Re(Atu)6](PF6)3 between 4000 and 400 cm (1.

zones, thiosemicarbazones and other related ligands bearing pharmacological interest.

TWAS. E.J.B. is a member of the Research Career from CONICET.

Acknowledgements This work has been supported by CONICYT/ BID and PEDECIBA (Uruguay), by CONICET and ANPCyT/PICT 06-06148 (Argentina) and by

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