Transition Metal Chemistry 29: 269275, 2004. 2004 Kluwer Academic Publishers. Printed in the Netherlands.

269

Synthesis and spectral studies on mononuclear complexes of chromium(III) and manganese(II) with 12-membered tetradentate N2O2, N2S2 and N4 donor macrocyclic ligands
Sulekh Chandra* and Rajiv Kumar Department of Chemistry, Zakir Husain College, University of Delhi, Jawaharlal Nehru Marg, New Delhi 110002, India
Received 15 July 2003; accepted 02 September 2003

Abstract Complexes of CrIII and MnII of general formula [Cr(L)X2] X and [Mn(L)X2] respectively were prepared from N2O2, N2S2 and N4 donor macrocyclic ligands. The complexes have been characterized by elemental analysis, molar conductance measurements, spectral methods (i.r, mass, 1H-n.m.r, electronic spectra and e.p.r.) and magnetic measurements. The macrocyclic ligands have three dierent donating atom cavities, one with two unsaturated nitrogens and the other two have saturated nitrogen, oxygen and sulphur atoms. The eect of dierent donor atoms on the spectra and ligand eld parameters is discussed. All the complexes show magnetic moments corresponding to a high-spin conguration. On the basis of spectral studies a six coordinated octahedral geometry may be assigned to these complexes. Introduction Enormous progress in macrocyclic chemistry has been made in the past decade [1, 2]. New macrocyclic ligand molecules have been designed and prepared with enhanced ability to encapsulate given metal ions selectively [3, 4]. Coordinated metal ions inuence the course of many complicated reactions occurring during metabolic activity in living organisms [5]. The coordination chemistry of manganese has achieved remarkable progress in the last decade due to the increased recognition of this metals role in biological systems [6, 7]. In this paper we report the synthesis and characterization of chromium(III) and manganese(II) complexes with N2O2, N2S2 and N4 donor macrocyclic ligands viz 2,3-diphenyl-1,4-diaza,7,10 dioxo,5,6:11,12-dibenzo [e,k]-cyclododeca-1,3 diene[N2O2] ane (L1), (Figure 1) 2,3-diphenyl-1,4,7,10-tetraaza-5,6:11,12-dibenzo [e,k]cyclododeca 1,3 diene [N4] ane (L2) (Figure 2) and 2, 3-diphenyl-1,4-diaza,7,10-dithia,5,6:11,12-dibenzo [e,k]cyclododeca-1,3 diene [N2S2] ane [L3] (Figure 3) containing aromatic head, and lateral units [8, 9]. An important aspect of the present work is the synthesis of three novel dibenzo-substituted Schi-base macrocycles derived from three dierent diamines containing aromatic rings with dierent donating atoms. Experimental All starting materials used were of analar grade, were purchased from Sigma Aldrich, and were used as received.
* Author for correspondence

Physical measurements Magnetic susceptibility measurements were carried out on a CAHN 2000 Faraday balance using Hg[Co(CNS)4] (vg 16.44 10)6 g cc)1 at 28 C) as the calibrating agent. Molar conductance measurements were carried out on a Leeds Northrup Conductivity Bridge 4995. I.r. spectra were recorded on a Perkin Elmer 137 instrument as KBr pellets. The electronic spectra of the complexes were recorded on a Shimadzu u.v. mini-1240 spectrophotometer in DMF solution. C and H analysis were carried out on a Carlo-Ebra 1106 elemental analyzer. Nitrogen was determined by Kjeldahls method. Mass spectra were carried out on JEOL, JMX, DX-303 mass spectrophotometers. 1H-n.m.r. spectra were recorded on a Bruker AVANCE 300 spectrometer at 100 kHz modulation at room temperature. E.p.r. spectra were recorded at room temperature on a Varion E-4 EPR spectrometer at ca. 9.1 GHz and 100 kHz eld modulation and phase sensitive detections and DPPH was used as marker. The macrocyclic ligands were prepared in three steps. Nitro compounds (Scheme 1) (a) 1,2-Di(o-nitrophenoxy)ethane o-NO2C6H4OH (4.78 g) in hot DMF (5.0 cm3) was treated slowly with K2CO3 (2.39 g). The resulting solution was boiled gently and BrCH2CH2Br (1.54 cm3) was added dropwise with constant stirring for 30 min. The mixture was then reuxed gently for 2 h and concentrated under reduced pressure. On pouring the solution into cold water a granular yellow solid precipitated. It

270 complete reaction had occurred. The heating was then reduced to keep the mass molten for a further use. The melt was poured into EtOH (50.0 cm3), the solid so obtained was washed with a mixture of Et2O (30.0 cm3), C6H6 (30.0 cm3) and 1 N NaOMe solution (10 cm3). It was recrystallized from ClCH2CH2Cl to give 1,2-di(onitrophenylamino)ethane (3.1 g) as bright orange needle shaped crystals. m.p. 192194 C. 1H-n.m.r.: (CDCl3) d 8.1 (2H, d), d 7.3 (2H, m), d 7.7 (2H, m), d 7.0 (H, d), d 4.0 (4H, NHACH2). The reaction is given below (Figure 5). Reduction of nitro compounds (Schemes 2a and b) The nitro products, 1,2-di(o-nitrophenoxy)ethane and 1,2,di(o-nitrophenylamino)ethane, were heated under a N2 atmosphere with 5% PdAC (0.5 g). N2H4 H2O (20.0 cm3) was added in (5 cm3) portions and the mixture reuxed until the solution become colourless (30 min). After ltration to remove the precipitate (if any), the solution was evaporated to dryness and the solid residue recrystallized from hot EtOH under a N2 atmosphere. A residue of white plates was obtained. m.p. 130132 C. 1H-n.m.r.: (CDCl3) d 6.3 (2H, d), d 7.1 (2H, m), d 6.6 (2H, m), d 7.0 (2H, d), d 4.0 (4H, OACH2) diamine(I) and 135136 C. 1H-n.m.r.: (CDCl3) d 6.3 (2H, d), d 7.1 (2H, m), d 6.6 (2H, d), d 6.7 (2H, d), d 3.0 (4H, m, NHACH2) diamine(II). The reactions are given below (Figures 6 and 7). 1,2-Di(o-aminophenylthio)ethane (Scheme 3) This diamine was prepared by heating o-HSC6H4NH2 (1.09 g) with absolute (99%) EtOH (3 cm3) containing Na (0.201 g). BrCH2CH2Br (0.372 cm3) in EtOH (1 cm3) was then added dropwise with constant stirring to the reuxing solution. The mixture was then cooled and poured into H2O (300 cm3). The solid mass so obtained, was ltered washed with H2O and dried. The product was recrystallized from EtOH, and a yellowish residue was obtained. m.p. 75 C. 1H-n.m.r.: (CDCl3) d 6.3 (2H, d), d 7.1 (2H, m), d 6.6 (2H, m), d 7.2 (2H, d), d 2.8 (4H, m, SACH2). The reaction is given below (Figure 8).

Fig. 1. Ligand (L1 ).

Fig. 2. Ligand (L2 ).

Fig. 3. Ligand (L3 ).

Structures of microcyclic ligands.

was ltered, washed with dilute aqueous NaOH, dried and recystallized from glacial MeCO2H, m.p. 169 170 C, 1H-n.m.r.: (CDCl3) d 8.1 (2H, d), d 7.3 (2H, m), d 7.7 (2H, m), d 7.0 (H, d), d 4.0 (4H, OACH2). The reaction is given below (Figure 4). (b) 1,2-Di(o-nitrophenylamino)ethane (Scheme 2) 1,2-Di(o-nitrophenylamino)ethane was prepared by heating BrC6H4NO2 (2.0 g) with 1,2,H2NCH2CH2NH2 (0.26 cm3). The mixture was stirred rigorously until

Fig. 4. 1,2-Di(o-introphenoxy)ethane (Scheme 1).

Fig. 5. 1,2-Di(o-introphenylamino)ethane (Scheme 2).

271 (I) Reduction of 1,2-di(o-nitrophenoxy)ethane

Fig. 8. 1,2-Di(o-aminophenylthio)ethane (Scheme 3).

Fig. 6. 1,2-Di(o-aminophenoxy)ethane (Scheme 2a).

(II) Reduction of 1,2-di(o-nitrophenylamino)ethane

reduced pressure and kept overnight. The white/white o crystals which formed were ltered, washed with EtOH and dried under vacuum over P4O10. (Yield: 71%); m.p. 172 C ligand (L1) (yield: 67%); m.p. 179 C for ligand (L2) and (yield: 70%) m.p. 182 C ligand (L3). (Found: C, 80.0; H, 5.0; N, 6.2. (L1) C28H22N2O2 calcd.: C, 80.4; H, 5.3; N, 6.7%. Found: C, 80.1; H, 5.3; N, 13.1 (L2) C28H24N4 calcd.: C, 80.7; H, 5.8; N, 13.4%. Found: C, 74.1; H, 4.3; N, 6.0 (L3) C28H22N2S2 calcd.: C, 76.6; H, 4.9; N, 6.2%) Figure 9.
1

H-n.m.r. spectra of macrocyclic ligands

Fig. 7. 1,2-Di(o-aminophenoxy)ethane (Scheme 2b).

Ligand (L1): d 7.27.3 (10H, m), d 6.9 (2H, d), d 7.1 (2H, m), d 6.6 (2H, m), d 7.0 (2H, d) d 4.0 (4H, OACH2). The mass spectrum of the ligand (L1) shows a peak at 417 amu. corresponding to the molecular ion (M++1). Mass spectrum, EIMS m/z (%) 417 (M+, 60), 350 (30), 222 (50), 147 (40), 105 (90), 77 (62), 58 (35). Ligand (L2): d 7.27.4 (10H, m), d 6.9 (2H, d), d 7.1 (2H, m), d 6.6 (2H, m), d 6.7 (2H, d) d 3.0 (4H, NHACH2). The mass spectrum of the ligand (L2) shows a peak at 415 amu.. corresponding to the molecular ion (M++1). Mass spectrum, EIMS m/z (%) 415 (M+, 6), 376 (4), 291 (15), 275 (20), 219 (19), 192 (80), 85 (100). Ligand (L3): d 7.27.24 (10H, m), d 6.9 (2H, d), d 7.1 (2H, m), d 6.6 (2H, m), d 7.27 (2H, d) d 4.0 (4H, m,

Macrocyclic ligands 2,3-Diphenyl-1,4-diaza,7,10-dioxo,5,6:11,12-dibenzo [e,k]-cyclododeca-1, 3 diene[N2O2] ane (L1), 2,3-diphenyl-1,4,7,10-tetraaza-5,6:11,12-dibenzo [e,k]-cyclododeca 1,3 diene [N4] ane (L2) and 2,3-diphenyl-1,4-diaza,7,10dithia,5,6:11,12-dibenzo [e,k]-cyclododeca-1,3 diene [N2S2] ane [L3] were obtained as described below. These ligands were characterized by elemental analysis, mass spectra, 1H-n.m.r. and i.r. spectra. To an EtOH solution (25 cm3) of benzyl (0.05 mol, 1.05 g), an EtOH solution (25 cm3) of 1,2-di(o-aminophenoxy)ethane or 1,2-di(o-aminophenylamino)ethane or 1,2-di(o-aminophenylthio)ethane (0.005 mol) was added in the presence of a few drops of conc. HCl and the resulting solution boiled under reux for 57 h. The solution was then concentrated to half its volume under

Fig. 9. Reaction mechanism of macrocyclic ligands.

272 SACH2). The mass spectrum of ligand (L3) shows a peak 449 amu.. corresponding to molecular ion (M++1). Mass spectrum, EIMS m/z (%) 449 (M+, 52), 421 (71), 402 (15), 370 (35), 250 (25), 185 (81), 51 (38). Preparation of complexes A hot EtOH, solution (20 cm3) of the hydrated metal salts, CrX3 xH2O or MnX2 xH2O (0.005 mol) (where ) X Cl , or SCN)) was added to a hot EtOH solution 3 (20 cm ) of the corresponding ligand (0.005 mol). The mixture was then reuxed on a water bath at 80 C for 57 h. On cooling a precipitate was obtained which was ltered, washed with EtOH and dried over P4O10 under vacuum. 1755 cm)1 shows the absence of ketonic groups. It conrms the elimination of water molecules and, as a result, cyclization takes places with formation of a macrocyclic ligand. In the i.r. spectra of L1 (1624 cm)1), L2 (1620 cm)1) and L3 (1608 cm)1) a new band appears in all the ligands corresponding the m(C@N) group. The i.r. spectra of these complexes show a moderate intensity absorption in the 15901610 cm)1 range attributed to the imine, m(C@N). This moderate intensity absorption band is showing a shift to the lower side in the complexes, suggesting coordination through the nitrogen of the m(C@N) group. The spectrum of ligand (L2) shows a band at 3320 cm)1 corresponding to m(NH) [10]. On complexation this band is shifted towards the lower side 3310 cm)1. This indicates diversion of the electron cloud from the nitrogen of the imidazole or amino group, thus resulting in a lowering of the NAH stretching frequency. In the i.r. spectra of L1, L2 and L3 PhAOACH2, PhANHACH2 and PhASACH2 group show bands in the 305485 cm)1 range. These bands are also shifted to the lower side after complexation of the macrocyclic ligands and conrm the complexation of the macrocyclic ligands. A new band appeared in the 310 490 cm)1 range in the spectra of chromium(III) and manganese(II) complexes. These weak bands can be assigned to 405 cm)1 m(MAO), 485 cm)1 m(MAN) and 305 cm)1 m(MAS) coupled with other lower vibrational modes of the ligand molecule [11, 12]. Far i.r. spectra also conrmed the MACl band in the range 300 320 cm)1 consistent with coordination of the halo group. Important i.r. bands of all complexes are recorded in Table 2.

Results and discussion All the complexes have compositions CrLX3 or MnLX2 (L ligands L1, L2 and L3 and X Cl) or SCN)). Chromium(III) complexes show molar conductances corresponding to 1:1 electrolytes, whereas the manganese(II) complexes are non-electrolytes (Table 1). The complexes may therefore be formulated as [CrLX2] X and [MnLX2] respectively. Related data are listed in Table 1. I.r. spectra The absence of an absorption at ca. 3400 cm)1 in the i.r. spectra of ligands shows that the free amino groups are absent, and the absence of a strong band at ca. 1675

Table 1. Characterization data for the CrIII and MnII complexes Complex Yield (%) M.p. (C) Molar conductance (W)1 cm2 mol)1) Colour Found (Calcd) (%)

M [Cr(L1)Cl2] Cl Cr C28H22N2O2 Cl3 [Cr(L2)Cl2] Cl Cr C28H24N4 Cl3 [Cr(L3)Cl2] Cl Cr C28H22N2 S2 Cl3 [Mn(L1)Cl2] Mn C28H22N2O2Cl2 [Mn(L1)(SCN)2] MnC30H22N4O2S2 [Mn(L2)Cl2] Mn C28H24N4Cl2 [Mn(L2)(SCN)2] MnC30H24N6S2 [Mn(L3)Cl2] Mn C28H22N2 S2Cl2 [Mn(L3)(SCN)2] MnC30H22N4S4 40 45 63 60 50 65 61 68 62 206 200 190 175 180 190 195 180 189 95.0 98.0 85.0 12.0 18.0 15.0 11.0 16.0 4.0 light green light green blackish green pale yellow yellow pale yellow yellow o white white 8.85 (9.0) 8.8 (9.0) 8.0 (8.5) 9.8 (10.1) 9.1 (9.3) 9.8 (10.1) 8.6 (8.85) 9.1 (9.5) 8.5 (8.6)

C 57.8 (58.3) 58.15 (58.5) 54.9 (55.2) 61.6 (61.8) 61.0 (61.1) 61.85 (62.0) 61.0 (61.3) 57.9 (58.3) 47.0 (47.1)

H 2.9 (3.8) 3.9 (4.2) 3.1 (3.6) 3.9 (4.0) 7.3 (7.8) 4.1 (4.5) 4.0 (4.1) 3.2 (3.8) 3.0 (3.2)

N 4.4 (4.9) 9.15 (9.75) 4.1 (4.16) 4.8 (5.15) 9.25 (9.5) 9.9 (10.3) 14.2 (14.3) 4.3 (4.9) 9.0 (9.1)

2,3-Diphenyl-1,4-diaza,7,10 dioxo,5,6:11,12-dibenzo [e,k]-cyclododeca-1,3 diene[N2O2] ane(L1), 2,3-diphenyl-1,4,7,10-tetraaza-5,6:11,12-dibenzo [e,k]-cyclododeca 1,3 diene [N4]ane (L2) and 2,3-diphenyl-1,4-diaza,7,10-dithia,5,6:11,12-dibenzo[e,k]-cyclododeca-1,3 diene[N2S2]ane [L3].

273
Table 2. I.r. spectral data of the ligands and their CrIII and MnII complexes Complex [Cr(L1)Cl2] Cl [Cr(L2)Cl2] Cl [Cr(L3)Cl2] Cl [Mn(L1)Cl2] [Mn(L1)(SCN)2] [MnCl2] [Mn(L2)(SCN)2] [Mn(L3)Cl2] [Mn(L3)(SCN)2] m(NH) cm)1 3320 3330 3325 m(C@N) cm)1 1627 1627 1607 1608 1607 1604 1609 1600 1595 m(MAN) cm)1 415 469 452 518 517 583 590 510 525 m(MAO) cm)1 404 410 401 m(MAS) cm)1 309 306 310 m(SCN) 2120 2110 2115

Bands due to anions The i.r. spectra of the thiocyanato complexes show a single sharp band at 20892083 cm)1 [13] suggesting that both thiocyanato groups are nitrogen-bonded, are in a similar environment and occupy an axial position. Therefore a six coordinated structure with tetradentate macrocyclic ligands may be suggested for these complexes and related data are listed in Table 2. Chromium(III) complexes Chromium(III) complexes exhibit magnetic moments, 3.773.81 B.M, at room temperature corresponding to three unpaired electrons. The moments are close to the spin only values, suggesting an octahedral geometry around the chromium ion [14]. The electronic spectra of the complexes recorded in DMF (hplc grade) show two bands in the 12,16515,552 and 18,62121,691 cm)1 ranges corresponding to 4 A2g(F) 4T2g(F) and 4A2g(F) 4T1g(F) transitions respectively. The transition 4A2g(F) 4T1g(P) is usually not observed in the visible region due to involvement of the charge transfer band. The visible region of the electronic spectra of the L1, L2 and L3 complexes show m1 at 12,360, 15,552 and 12,165 cm)1, due to the presence of dierent donating atoms [15]. The position of the bands indicates that these complexes exhibit octahedral geometry, consistent with D4h symmetry around the metal ion [16]. Related data are listed in Table 3.

Ligand eld parameters Various ligand eld parameters (Dt, DT, Dqy, Dqz, Ds, Dq, Dqxy, B, C, k and b) have been calculated [17, 18] for the chromium(III) complexes listed in Table 4. The values of ligand eld parameters are consistent with octahedral geometry for the complexes. The rst (m1) and second transition (m2) directly give the values of 10Dq and 10Dqxy. The Racah interelectronic repulsion parameter B is calculated from the relation. 2 B 2m 2 1 3m1 m2 m2 =15m2 27m1 . The nephlauxetic parameter b is obtained using the relation b B(complex)/B(free ion), where B(free ion) 918 cm)1. The b values indicate that there is appreciable covalent character in the metal ligand r bond. Related data are listed in Table 3.

E.p.r. spectra The e.p.r. spectra of the complexes were recorded for polycrystalline samples at room temperature and their values are reported in Table 3. The spectra of powdered samples of the complexes show a broad line. The g values are calculated from the expression: g 2:00231 4k=10Dq where k is the spin orbit coupling constant for the metal ion. Owen [19] noted that the reduction of spinorbit coupling constant for the free ion value of 90 cm)1 for chromium(III) can be employed as a measure of metal ligand covalency. The value of k

Table 3. E.p.r. electronic, spectral and magnetic moment data of the CrIII complexes Complex [Cr(L1)Cl2] Cl [Cr(L2)Cl2] Cl [Cr(L3)Cl2] Cl Dq (cm)1) 1686 1862 2169 B (cm)1) 747 737 605 C (cm)1) 2988 2948 2420 b 0.81 0.80 0.65 le B.M. 3.77 3.81 3.80 g 1.98 1.95 1.99

Table 4. Ligand eld (cm)1) parameters of the CrIII complexes Complex Dq (cm)1) B (cm)1) C (cm)1) b 747 737 605 2988 2948 2420 0.81 0.80 0.65 LFSE DT/Dq kJ/mol)1 241.7 267.0 311.0 0.114 0.091 0.970 Dt
y Dq (cm)1) z Dq (cm)1)

Ds (cm)1) 5901 5806 7513

DS 8901 5806 7513

[Cr(L1)Cl2] Cl 1686 [Cr(L2)Cl2] Cl 1862 [Cr(L3)Cl2] Cl 2169

743.7 737.8 701.6

2537 2507 2783

585.0 571.0 951.0

44.04 45.53 53.87

274 indicates that the complexes under study have substantial covalent character. It is possible to dene the covalency parameter analogous to the nephelauxetic parameter which is the ratio of the spin orbit coupling constant for the complex and free ion [20]. Manganese(II) complexes These complexes show magnetic moments in the 5.90 5.96 B.M. range at room temperature [21]. In the complexes the intensities of electronic transitions from the ground state 6S to states of fourfold multiplicity are very weak, since manganese(II) has a d5 electronic conguration. The electronic spectra of complexes show bands at 17,10017,850 cm)1 (m1) 24,15024,240 cm)1 (m2), 28,54028,800 cm)1 (m3) and 31,000 cm)1 (m4) [22]. These bands may be assigned as 6A1g 4T1g(4G) (m1), 6 A1g 4Eg (4G) (m2), 6A1g 4Eg (4D) m3 and 6 A1g 4T1g (4P) (m4) transitions respectively. The ligand eld parameter, values Dq, B, C, b, F4, F2 and Hx are calculated and given in Table 5.
6

g values are given in Table 5. The polycrystalline samples give one broad isotropic signal centered at ca. the free electron g-value (g0 2.0023). In DMF solution the e.p.r. spectra of the complexes clearly show that, in this solvent, the complexes existed as monomeric units. The nuclear magnetic quantum numbers MI corresponding to these lines are )5/2, )3/2, )1/2, 1/2, 3/2, 5/2 from low to the high eld [2628].

Acknowledgements One of the authors (Kumar) gratefully thanks my younger brother Bitto for motivation. Thanks are also due to the Principal, Zakir Husain College, for providing laboratory facilities, the UGC New Delhi for nancial assistance, and the USIC Delhi University for recording i.r. spectra. Thanks are also due to the SSPL solid state physics lab for recording magnetic moments and the IIT Bombay for recording e.p.r. spectra.

A1g ! 4 Eg; 4 A1g 4 G 10B 5C A1g ! 4 T1g 4 P 17B 5C

The energies of these transitions are independent of the crystal eld splitting energy and depend [23] only on the parameters B and C. Dq can be evaluated with the help of the energy level due [24] to the 6A1g 4T1g (4G) transition. Slater Condon parameters F2 and F4 are related to the Racah parameters B and C as follows B F2 5F4 ; C 35F4. The electronelectron repulsion in the complexes is less than that in the free ion, resulting in an increased distance between electrons and thus an eective increase in the size of the orbitals. On increasing delocalization the value of b decreases and is less than one in the complexes. The numerical value 786 cm)1 for the B of the free manganese(II) ion has been used to [25] calculate the value of b. The calculated values of b (0.790.83) and Hx indicate that the complexes under study have appreciable covalent character. E.p.r. spectra The e.p.r. spectra of the complexes have been recorded using polycrystalline samples at room temperature; their
Table 5. Ligand eld (cm)1) parameters of the MnII complexes Complex [Mn(L1)Cl2] [Mn(L1)(SCN)2] [Mn(L2)Cl2] [Mn(L2)(SCN)2] [Mn(L3)Cl2] [Mn(L3)(SCN)2] Dq (cm)1) 1785 1765 1750 1745 1710 1735 B (cm)1) 627 481 651 588 614 735 C (cm)1) 3576 3984 3546 2665 3614 2307 b 0.79 0.81 0.82 0.83 0.78 0.81 F4 102 113 101 76.0 103 65.0 Hx 3.00 2.70 2.57 2.40 4.00 2.70 F2 1137 1046 1156 968 1229 1060 le B.M. 5.91 5.98 5.85 5.91 6.00 6.96 g 1.99 1.97 1.96 1.94 1.93 1.95

Proposed structure of the CrIII and MnII complexes.

275 References
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TMCH 5755