Spectrochimica Acta Part A 78 (2011) 14081415

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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

journal homepage: www.elsevier.com/locate/saa

Reactivity of tris(acetylacetonato) iron(III) with tridentate [ONO] donor Schiff base as an access to newer mixed-ligand iron(III) complexes
Chira R. Bhattacharjee a, , Pankaj Goswami b , Harun A.R. Pramanik a , Pradip C. Paul a , Paritosh Mondal a
a b

Department of Chemistry, Assam University, Silchar 788011, Assam, India Department of Chemistry, Silchar Polytechnic, Silchar 788015, Assam, India

a r t i c l e

i n f o

a b s t r a c t
Two new mixed-ligand iron(III) complexes, [Fe(Ln )(acac)(C2 H5 OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac)3 ] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H2 L1 ) or 2-aminobenzoic acid (H2 L2 ). The thermal study (TGADTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(Ln )(acac)X] (n = 1, 2; X = Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UVvis, solution electrical conductivity, FAB mass, 1 H and 13 C NMR spectroscopy. Room temperature magnetic susceptibility measurements ( eff 5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response ( Ep > 100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential (E1/2 ) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level. 2011 Elsevier B.V. All rights reserved.

Article history: Received 17 September 2010 Received in revised form 11 January 2011 Accepted 17 January 2011 Keywords: Mixed-ligand iron(III) complexes Tridentate Schiff base DFT Cyclic voltammetry

1. Introduction Schiff base metal complexes, prepared in situ or isolated as stable solids are considered as simple and suitable candidate for catalytic application [13]. Tridentate Schiff base ligands, in particular, have received extensive attention in different catalytic reactions [4]. Iron complex with a tridentate Schiff base, accessed in situ from [Fe(acac)3 ] has been shown to act as catalyst for enantioselective oxidation of suldes to sulfoxides [5]. Synthesis of a mixed-ligand unsymmetrical tridentate Schiff base donor complex of iron(III), [FeL(acac)(C2 H5 OH)] has recently been accomplished from the reaction of [Fe(acac)3 ] with tridentate [ONO] donor Schiff base (L) and the performance of this complex in sulde oxidation catalysis has also been assessed [6]. Formation of a novel dinuclear iron(III) complex, from the reaction of a tripodal ligand with [Fe(acac)3 ], has been reported rather recently [7]. Reactions of [Fe(acac)3 ] with hydrogen halide (HX) to access newer mixed halo acctylacetonato iron(III) complexes have also been documented [8]. Being inexpensive and environmentally benign, iron(III) acetylacetonate catalyzed cross-coupling reactions is a recurring theme of current research [912]. Ligand replacement reaction of metal acetylacetonates depends, among other factors, upon the denticity,

Corresponding author. Tel.: +91 9435175671; fax: +91 3842270803. E-mail address: crbhattacharjee@rediffmail.com (C.R. Bhattacharjee). 1386-1425/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.saa.2011.01.019

electronic and steric properties of ligands as well [1316]. Solvent molecules usually bound to metal acetylacetonates are readily exchanged with neutral N-donor molecules such as ammonia, pyridine, imidazole, etc. to yield complexes of interesting structural and chemical properties [1719]. Metal acetylacetonates as general precursors for synthesis of transition metal oxide nanomaterials is another attractive synthetic option that drew lot of current attention [20,21]. That metal ions in many protein and enzyme are surrounded by unsymmetrical ligand donor environment has also triggered interest in design, synthesis and application of such ligands. Thus mixed-ligand Schiff base complexes are of acknowledged importance owing to their potential applications in photoluminescence, catalysis, magnetism, molecular architecture, material chemistry and therapeutic effects [2225]. Very recently, we have reported aquated iron(III) complex of a quadridentate Schiff base and its ligand exchange reactions with inorganic donor anions yielding mixed-ligand complexes [26] and some mixedligand mono- and dinuclear iron(III)-tridentate [ONO] donor Schiff base complexes [27]. As a sequel, we report herein, reactivity of [Fe(acac)3 ] with dibasic tridentate [ONO] donor Schiff base ligands derived from 2hydroxynaphthaldehyde with 2-aminophenol or 2-aminobenzoic acid leading to the formation of desired mixed-ligand complexes of the type, [Fe(Ln )(acac) (C2 H5 OH)] (L = L1 or L2 ). The weakly bound ethanol at the axial site has been exploited to create substitution with neutral N-donor molecules, imidazole, benzimidazole and

C.R. Bhattacharjee et al. / Spectrochimica Acta Part A 78 (2011) 14081415

1409

H C O OH + H2N OH

MeOH reflux -H2O

HC N OH

OH

[Fe(acac)3] EtOH reflux, 3h

HC

NEtOH O Fe O O H3C O CH3

+2Hacac

Schiffbase (H2L1)

[Fe(L1)(acac)(EtOH)] (1)

H C O OH + H2N COOH

MeOH reflux -H2O

HC N OH

COOH

Schiffbase (H2L2)

[Fe(acac)3] EtOH reflux, 3h

HC N O

EtOH Fe O

C O O

+2Hacac
CH3

H3C

[Fe(L2)(acac)(EtOH)] (2)
Scheme 1.

pyridine to access array an of newer mixed-ligand iron(III) complexes.

2. Experimental 2.1. General Solvents used were puried by the standard methods described in the literature [28,29]. Commercially available pure samples of 2-hydroxy-1-napthaldehyde, 2-amino phenol and 2-aminobenzoic acid were obtained from Fluka A.G., Switzerland and used as received. Tris(acetylacetonato) iron(III) was prepared by standard procedure [30] and recrystallized before use. Micro analytical (C, H, N) data were obtained with a PerkinElmer model 240C elemental analyzer. Solid state infrared spectra were recorded with a PerkinElmer/spectrum BX series FT-IR spectrophotometer using KBr pellets in the range 4000400 cm1 . Electronic spectra were recorded in dichloromethane solution on a Shimadzu 1600 PC UV-VIS spectrophotometer in 200800 nm range. NMR spectra were acquired from Bruker Advance 300 MHz FT NMR spectrophotometer using CDCl3 as solvent and TMS as internal standard. FAB mass spectra were recorded on JEOL SX-102 Mass spectrometer. TGA/DTA was carried out on a PYRIS DIAMOND thermal analyzer under a dynamic ow of nitrogen (100 mL/min) and heating rate of 10 C/min from ambient temperature to 1000 C. Molar conductance of the Schiff base complexes was measured on Systronics direct reading conductivity meter type CM-82. Magnetic measurements were carried out at room temperature by the Gouy method using Hg[Co(SCN)4 ] as calibrant. Electrochemical behavior of the complexes were examined by cyclic voltammetry at room temperature in acetonitrile solution of ca. 103 M using TBAP as supporting electrolyte under dry N2 atmosphere on a PC controlled CHI model 660C electrochemical workstation. A Pt disk, a Pt wire auxiliary electrode and an aqueous SCE were used in a three electrode conguration.

2.2.1. H2 L1 Yield: 78%; Calcd.: C, 77.56; H, 4.94; N, 5.32. Found: C, 77.24; H, 4.78; N, 5.38. IR (cm1 ): 3415 br. (OH), 1615 (C N); UVvis ( max , nm/, M1 cm1 ): 340 (18,800), 306 (15,700), 274 (6100), 246 (59,400); 1 H NMR (CDCl3 , TMS, , ppm): 15.59 (s, 1H, OH); 15.58 (s, 1H, OH); 8.04 (s, 1H, HC N); 6.897.72 (m, 10H, phenyl proton); 13 C NMR (CDCl3 , TMS, , ppm): 107.34, 116.01, 116.84, 117.90, 119.41, 122.53, 124.42, 125.75, 126.25, 127.56, 128.62, 133.27, 137.23, 138.84, 148.47, 149.03, 163.72; MS (FAB, m/z): 263 [M]+ . 2.2.2. H2 L2 Yield: 73%; Calcd.: C, 74.23; H, 4.47; N, 4.81. Found: C, 74.46; H, 4.62; N, 5.08. IR (cm1 ): 3420 br. (OH), 1685 (C O), 1612 (C N); UVvis ( max , nm/, M1 cm1 ): 340 (15,600), 306 (13,300), 277 (2800), 246 (49,600); 1 H NMR (CDCl3 , TMS, , ppm): 13.04 (s, 1H, COOH); 10.04 (s, 1H, OH); 8.45 (s, 1H, HC N); 6.567.84 (m, 10H, phenyl proton); 13 C NMR (CDCl3 , TMS, , ppm): 114.89, 115.84, 116.94, 118.32, 124.32, 126.14, 127.73, 128.54, 128.65, 131.42, 132.06, 132.98, 133.10, 137.99, 138.48, 150.32, 162.82, 192.84; MS (FAB, m/z): 291 [M]+ . 2.3. Synthesis of Schiff base complexes 2.3.1. Synthesis of complexes of the type [Fe(Ln )(acac)(EtOH)] (n = 1 or 2) [Fe(acac)3 ] (1 mmol, 0.353 g) solution in ethanol (20 mL) was added to a warm stirred solution of the corresponding Schiff base H2 L1 (1 mmol, 0.263 g) or H2 L2 (1 mmol, 0.291 g) in 20 mL ethanol. The reaction mixture was reuxed for 3 h and then concentrated to half its volume. On cooling, dark brown microcrystalline solid formed was ltered, washed with cold ethanol, recrystallized from methanoldichloromethane and dried in vacuum over anhydrous CaCl2 (Scheme 1). 2.3.2. Synthesis of complexes of the type [Fe(Ln )(acac)X] (X = Im, BIm or Py) The complex, [Fe(Ln )(acac)(EtOH)] (1 mmol) was dissolved in ethanol (20 mL) and was added to an ethanolic solution (10 mL) of imidazole, benzimidazole or pyridine (1 mmol) separately. The reaction mixture was stirred on a water bath for 40 min. The resulting brown micro crystalline solid was ltered, washed with cold ethanol, recrystallized from methanoldichloromethane and dried in vacuum over anhydrous CaCl2 (Scheme 2).

2.2. Synthesis of Schiff base ligands (H2 L1 and H2 L2 ) The Schiff bases were synthesized by reuxing methanolic solution of 2-aminophenol (10 mmol, 1.09 g) or 2-aminobenzoic acid (10 mmol, 1.37 g) with 2-hydroxy-1-napthaldehyde (10 mmol, 1.72 g) in 20 mL methanol in presence of few drops of acetic acid. On cooling, the yellow crystals formed were ltered and washed with ether. Recrystallization from ethanol afforded pure Schiff bases.

1410
NH N

C.R. Bhattacharjee et al. / Spectrochimica Acta Part A 78 (2011) 14081415

EtOH, Stirr, w.b.40min

H N
n [FeL (acac)(EtOH)]

[FeLn (acac)Im] (3, 4)

(n=1 or 2)

EtOH,Stirr, w.b.40min
N

[FeLn (acac)BIm](5, 6)

EtOH,Stirr, w.b.40min
Scheme 2.

[FeLn (acac)Py] (7, 8)

3. Results and discussion The synthesized Schiff base ligands H2 L1 and H2 L2 and all the iron(III) complexes are stable to air and moisture and are soluble in organic solvents like methanol, ethanol, chloroform, dichloromethane, DMF and DMSO. The analytical data (Table 1) are in good agreements with the proposed structures of the Schiff base ligands and their complexes. The dibasic tridentate Schiff base ligands, it was conjectured, would displace two acetylacetonato ligands occupying four coordination sites in the tris-chelate [Fe(acac)3 ] complex in a 1:1 stoichiometric reaction leaving one site potentially vacant or solvated. The strategy worked well leading to the successful synthesis of solvated six coordinate iron(III) complexes. Reactions with neutral donor molecules led to facile substitution of the weakly held ethanol molecule incorporated from the reaction solvent affording newer mixed-ligand complexes providing at the same time evidence for the solvent coordination. Pertinent here is to mention that rather similar type of tridentate [ONO] donor ligand systems derived from acetylacetone has earlier been shown to yield iron(III) complexes of different composition and geometry [27]. Schiff base ligands based on aminophenol led to binuclear square pyramidal iron(III) complex while those based on aminocarboxylic afforded mononuclear distorted four coordinate iron(III) complexes. Use of different metal source, ferric chloride in previous work [27] and tris(acetylacetonato) iron(III) complex in the present work appears one obvious reason for such observed differences. 3.1. Infrared spectra The characteristic FT-IR bands of the complexes are summarized in Table 2. The infrared spectra of the ligands showed a broad band around 3420 cm1 due to OH . Absence of this fea-

ture in the complexes attested coordination via phenolic-O while a rather broad peak at ca. 3445 cm1 in both the complexes 1 and 2 assignable to OH is probably due to the adsorbed or weakly bound ethanol molecule which was conrmed by thermal studies. Complete absence of such broad peaks in the case of complexes 38 which lack coordinated ethanol lends further credence to this notion. Bands at ca. 1615 cm1 attributed to C N stretching in the ligands shifted to lower wave number in the complexes indicating coordination of the azomethine nitrogen atom [31]. Two weak bands observed in all the complexes in the range of 502595 cm1 and 443520 cm1 are assigned to FeN and FeO stretching, respectively. The Schiff base thus coordinate in a tridentate fashion through azomethine-N and two phenolic-O. The coordinated imidazole and benzimidazole group in the complexes 3, 4, 5 and 6 showed NH in the region 34013421 cm1 along with other characteristics vibrational modes. The band at 3050 cm1 in the complexes 7 and 8 may be assigned to CH of coordinated pyridine group. Characteristics ring modes of pyridine were also observed in these complexes. 3.2. Electronic spectra UVvisible spectra of the compounds were recorded in dichloromethane (Table 2). A weak band in the region 405519 nm in the complexes is anticipated to arise from partially allowed 6 A excited states dd transitions conrming the occurrence of 1 high spin iron(III) centre. The charge transfer band in the region 361381 nm in the complexes is attributed to a phenolate (p ) iron(III) (d * ) transition [32,33]. The intense higher-energy bands in the range of 231340 nm in the ligands as well as complexes are attributed to intraligand n * and * transitions [34]. The band 340 nm presumably owing to intraligand charge transfer transition of the ligand, particularly remain unaffected in the complexes. 3.3. NMR spectra The NMR spectra of Schiff base ligands were recorded in CDCl3 at room temperature. The 1 H NMR spectral data (vide infra) of the ligands showed a multiplet in the region 6.567.84 ppm assignable to protons of the benzene ring. A sharp singlet at 8.04 and 8.45 ppm in the ligands H2 L1 and H2 L2 respectively is due to azomethine protons (CH N). The two singlets in downeld region are attributed to hydroxyl protons. The 13 C NMR spectra of the ligands are concordant with different types of magnetically non-equivalent carbons. The peak around

Fig. 1. Mass spectra of the complex [Fe(L1 )(acac)(EtOH)].

Table 1 Analytical data and physical properties of complexes. Complexes Colour Yield (%) ( C) 65 63 60 59 66 68 58 61 Decomp. temp. 238 247 251 260 258 270 244 255 Elemental analysisa (%) C [Fe(L1 )(acac)(EtOH)] [Fe(L2 )(acac)(EtOH)] [Fe(L1 )(acac)Im] [Fe(L2 )(acac)Im] [Fe(L1 )(acac)BIm] [Fe(L2 )(acac)BIm] [Fe(L1 )(acac)Py] [Fe(L2 )(acac)Py]
a

Mass peak m/z N 3.28(3.03) 2.68(2.85) 8.91(8.67) 8.28(8.20) 7.90(7.87) 7.19(7.47) 5.88(5.66) 5.21(5.35) M 12.02(12.15) 11.30(11.45) 11.68(11.57) 10.85(10.93) 10.63(10.49) 10.01(9.96) 11.19(11.31) 10.84(10.71) 461 489 484 512 534 562 495 523

cm2 mol1 )

eff

(B.M.) 12.3 16.8 19.4 14.9 22.3 25.1 17.8 20.5 5.86 5.83 5.94 5.82 5.84 5.90 5.98 5.93

H 4.96(5.19) 5.01(4.88) 4.45(4.54) 4.41(4.29) 4.61(4.49) 4.40(4.27) 4.47(4.65) 4.63(4.40)

Dark brown Dark brown Brown Brown Brown Brown Pale brown Pale brown

62.12(62.34) 61.40(61.22) 61.65(61.98) 60.29(60.63) 65.29(65.17) 64.23(64.06) 65.65(65.45) 64.04(64.24)

C.R. Bhattacharjee et al. / Spectrochimica Acta Part A 78 (2011) 14081415

Calculated values are given in parentheses.

Table 2 FT-IR (KBr, cm1 ) and UVvis [ Complexes [Fe(L1 )(acac)(EtOH)] [Fe(L2 )(acac)(EtOH)] [Fe(L1 )(acac)Im] [Fe(L )(acac)Im] [Fe(L1 )(acac)BIm] [Fe(L2 )(acac)BIm] [Fe(L )(acac)Py]
1 2 OH

max ,

nm (, M1 cm1 )] spectral data of complexes.

NH CH C O C N C N FeN FeO

(EtOH) 3447 3440

(Im/BIm) 3421 3401 3410 3401

(Py) 3050 1658 1665 1671

(coord) 1601 1597 1599 1597 1606 1597 1598

(cyclic) 1612 1610 1617 1610 1608 550 502 561 550 595 561 561 495 458 506 498 443 502 520

Ring modes of coordinated Im/BIm/Py 1541, 1508, 1457, 1341 1541, 1505, 1429, 1327 1510, 1478, 1459, 1440, 1425 1522, 1482, 1470,1439, 1420 1573, 1436, 639, 473

dd band 405(1200) 415(1400) 503(1889) 519(860) 405(1200) 408(1300) 468(980)

Charge transfer band 368(2200), 340(17000), 306(14200), 246(51200) 368(2600), 340(16500), 306(13700), 246(49990) 364(5260), 311(5620), 244(13260) 309(26130), 257(40000), 237(40000) 361(11000), 340(13500), 306(14200), 257(27200) 340(14610), 306(13190), 314(12540), 290(11980) 381(6590), 340(8940), 318(7240), 250(18300), 231(22600) 340(5770), 314(5590), 292(5700), 256(21890), 231(21460)

[Fe(L2 )(acac)Py]

3045

1654

1601

1614

554

512

1586, 1410, 647, 474

496(1040)

1411

1412

C.R. Bhattacharjee et al. / Spectrochimica Acta Part A 78 (2011) 14081415

Fig. 2. Mass spectra of the complex [Fe(L2 )(acac)(EtOH)].

163 ppm in both the ligands is due to azomethine carbon (CH N). Carbon atom of the carboxylic group (COOH) in H2 L2 has been observed at192.84 ppm with the carbon atoms of the benzene ring occurring over a broad range of 107150 ppm.

3.5. Thermal study Thermal analysis of the complex [Fe(L1 )(acac)(EtOH)] was carried out by TG and DTA technique. The complex underwent three steps decomposition (Fig. 3). The rst step (214292 C) with d.t.g. peak at 278 C showed a weight loss of 11.24% (calcd. 9.25%) that corresponds to the loss of labile ethanol molecule. The second step (464535 C) and third step (603628 C) with d.t.g. peak at 515 and 615 C, respectively, corresponds to loss of acetylacetone and partial decomposition of the Schiff base ligand. The exothermic change in 495612 C with d.t.a. peak at 542 C is related to the decomposition of the Schiff base ligand molecule (Fig. 4). 3.6. Molar conductance The solution electrical molar conductances of the complexes in DMSO (103 M) are in the range 12.325.1 1 cm2 mol1 , consistent with the non-electrolytic nature of the complexes [35]. 3.7. Magnetic measurements All iron(III) complexes exhibited magnetic moment values in the range of 5.985.83 B.M. (Table 1), in accordance with an octa-

3.4. Mass spectra The mass spectra of the compounds were recorded in FAB ionization mode. The molecular ion peak of the ligands H2 L1 and H2 L2 at m/z 263 and 291, respectively, and other fragments observed were in good agreement with the proposed formula. The molecular formula [Fe(L1 )(acac)(EtOH)], [Fe(L2 )(acac)(EtOH)], [Fe(L1 )(acac)Im], [Fe(L2 )(acac)Im], 1 2 1 [Fe(L )(acac)BIm], [Fe(L )(acac)Py] and [Fe(L )(acac)BIm], [Fe(L2 )(acac)Py] suggested for the complexes were conrmed by the observed peak at m/z 461, 489, 484, 512, 534, 562, 495 and 523 respectively. The rst molecular ion fragmentation step for the complexes [Fe(L1 )(acac)(EtOH)] (Fig. 1) and [Fe(L2 )(acac)(EtOH)] (Fig. 2) corresponds to the loss of ethanol moiety resulting in formation of the fragment [Fe(L1 )(acac)]+ (m/z = 415) and [Fe(L2 )(acac)]+ (m/z = 443), respectively corroborating the occurrence of ethanol in the complex.

Fig. 3. TGA graph of the complex [Fe(L1 )(acac)(EtOH)].

C.R. Bhattacharjee et al. / Spectrochimica Acta Part A 78 (2011) 14081415

1413

Fig. 4. DTA graph of the complex [Fe(L1 )(acac)(EtOH)].

hedral high spin Fe(III) (d5 ) centre with orbital moment quenched [34,36]. 3.8. Cyclic voltammetry Electrochemical behavior of the ligands and two representative complexes viz. [Fe(L1 )(acac)(EtOH)] and [Fe(L2 )(acac)(EtOH)] were examined by cyclic voltammetry in anhydrous acetonitrile solution (103 M) containing 0.1 M tetrabutyl ammonium perchlorate (TBAP) as supporting electrolyte in the potential range of 1.2 to 1.2 V vs. SCE at 100 mV s1 scan rate (Table 3). The free ligands did not show any responses in the potential range scanned implying their redox innocent behavior. The complexes exhibited quasireversible one electron response ( Ep > 100 mV) corresponding to Fe(III)/Fe(II) couple with half wave potential (E1/2 ) 0.012 and 0.0575 V, respectively, for the complex [Fe(L1 )(acac)(EtOH)] and [Fe(L2 )(acac)(EtOH)] (Figs. 5 and 6). A relatively low E1/2 values suggest easy redox susceptibility of the complexes [37]. Quite interestingly, our previous work on iron(III) complexes containing tridentate [ONO] donor Schiff base ligand also showed quasireversible electrochemical behavior under identical conditions with much lower Ep values and negative anodic peak potential [27]. Pertinent here is to mention that quasi-reversible electrochemical behavior of iron(III) complexes containing Schiff bases are well documented [26,3840]. 3.9. Quantum chemical calculations All calculations were carried out using DMol3 program package [41]. Quantum-chemical calculations of two selected compounds viz. [Fe(L1 )(acac)(EtOH)] and [Fe(L1 )(acac)(Im)] were performed by open-shell density functional theory (DFT) using BLYP/DNP functional. Starting from the experimentally determined spin free iron(III) octahedral environment, full optimizations of the complexes were carried out. The sextet spin state was found to be energetically more stable than the singlet state, attesting the
Table 3 Electrochemical data of the selected complexes. Compounds [Fe(L )(acac)(EtOH)] (1) [Fe(L2 )(acac)(EtOH)] (2)
1

Fig. 5. Cyclic voltammogram of the complex [Fe(L1 )(acac)(EtOH)].

high-spin conguration suggested by magnetic susceptibility measurements. The energy optimized structures of the complexes (Figs. 7 and 8) and the geometrical parameters (Table 4) suggest a distorted octahedral structure. Interestingly, the ironoxygen

Ep a (V) 0.682 0.806

Ep c (V) 0.707 0.691

Ep (V) 1.389 1.497

E1/2 (V) 0.012 0.0575

Fig. 6. Cyclic voltammogram of the complex [Fe(L2 )(acac)(EtOH)].

1414 Table 4 Structurally signicant geometrical parameters. Bond distances (A) Bond type Fe(1)N(1) Fe(1)O(1) Fe(1)O(2) Fe(1)O(3) Fe(1)O(4) Fe(1)O(5) Fe(1)N(2) [Fe(L )(acac)(EtOH)] 2.122 2.034 2.091 2.075 2.143 2.576
1

C.R. Bhattacharjee et al. / Spectrochimica Acta Part A 78 (2011) 14081415

Bond angles ( ) [Fe(L )(acac)(Im)] 2.112 2.038 2.097 2.091 2.133 2.000
1

Bond type N(1)Fe(1)O(1) N(1)Fe(1)O(2) O(1)Fe(1)O(3) O(2)Fe(1)O(3) N(1)Fe(1)O(4) N(1)Fe(1)O(5) N(1)Fe(1)N(2)

[Fe(L1 )(acac)(EtOH)] 87.4 79.6 97.2 95.5 95.3 91.6

[Fe(L1 )(acac)(Im)] 87.4 80.2 97.3 95.1 90.1 95.9

4. Conclusion Mixed-ligand Schiff base complexes of the type [Fe(Ln )(acac)(EtOH)] have been synthesized from the reaction of tris(acetylacetonato) iron(III) and dibasic tridentate Schiff base ligand and characterized by physico-chemical methods. The labile ethanol molecule at the axial coordination site of the complexes incorporated from the reaction solvent is readily replaced by neutral donor molecules leading to newer mixed-ligand iron(III) complexes. Magnetic measurements and conductivity studies support a high spin non-electrolytic nature of all the complexes. Cyclic voltammetric studies revealed quasi-reversible redox behavior of the complexes with peak separation Ep (>100 mV) and low half wave potential suggested easy redox susceptibility. The TGADTA analysis data are consistent with the proposed structures and provided unambiguous evidence for ethanol coordination. Quantum chemical DFT study revealed six-coordinate distorted octahedral structure of the complexes with small HOMOLUMO energy gap. The synthetic strategy adopted is anticipated to open up newer avenues for accessing vast array of neutral and anionic mixed-ligand complexes containing weakly coordinated solvent molecules. Such compounds exhibit facile ligand substitution reactions thus possessing immense catalytic potential. Acknowledgements The authors thank to SAIF, NEHU, Shillong; SAIF, STIC, Kochi; CIF, IIT, Guwahati and SAIF, CDRI, Lucknow, India for providing analytical and spectral results. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] Fig. 8. Six coordinate distorted octahedral structure of [Fe(L )(acac)(Im)]; DFT (BLYP/DNP) optimized geometry.
1

Fig. 7. Six coordinate distorted octahedral structure of [Fe(L1 )(acac)(EtOH)]; DFT (BLYP/DNP) optimized geometry.

in [Fe(L1 )(acac)(EtOH)] is quite (ethanol) bond length (2.576 A) longer the ironnitrogen (imidazole) bond length (2 A) in [Fe(L1 )(acac)(Im)] validating the labile nature of metalethanol linkages. The rest geometrical parameters in both the complexes are almost similar. The HOMO and LUMO energies of the complex [Fe(L1 )(acac)(EtOH)] are found to be 3.765 and 3.061 eV, respectively, while that for the complex [Fe(L1 )(acac)(Im)] are 3.857 and 2.962 eV, respectively. The small HOMOLUMO energy gap (0.80 eV) accounts for the low redox potentials of the complexes.

[19]

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