Indian Journal of Chemistry Vol. 43A, September 2004, p~. 1853-1 862

Synthesis, characterization and reactions of metal complexes of 2-(1-formyl-ferrocene )thiazoline and 2-methyl-2-(1-ferrocene )thiazoline

Kamalendu Dey*, Sanjib Mukhopadhyay & Saikat Sarkart

Depart ment of Chemistry, Uni versity of Kalyani , Kalyani 74 1 235, India Email: kdey@ klyuni v.ernet.in -

Received 19 January 2004; revised 9 JUli e 2004

Reaction of I-formylferrocene and l-acetylferrocene with 2-aminoethanethiol yielded 2-(l -formylferrocene)thi azoline (Ffthz) and 2-methyl-2-( I-ferrocene)thi azoline (M fth z) rather than the corresponding schi ff bases 2-(I-formylferrocene)­i mi noethaneth iol (H Ffi met hoI ) and 2-Methy 1-2-( 1- fe rrocene) i mi noethanethiol (HM fi methol), respecti vely. The reaction of Ffthz and Mfthz with M(OAc)2. nH20 (M = Co, Ni, Cu, Zn, Cd), MC I2· nH 20 (M = Cu, Co, Ni ), M(N03h nH20 (M = Cu, Co, Ni), Me2SnCI2, MeSnCl J , (TC-C, H')2MC I2 (M = Ti, Zr), (TC-C, H, )TiCI3' (TC-C, H5)TiCI2(OMe) and TiCI2(OMeh, under varied react ion conditi ons afforded the corresponding schiff base complexes of the metal ions. Monoanion of the schi ff base (Ffi methol)l- or (Mfi methol)l- fun ctions as bidentate NS donor li gand in the complexes. Reactions of [MeS n(Ffi methol)2Clj and [(TC-C., H,)Ti(Ffi methol)2CIj, iso lated in thi s study, with MeSH, Me2NSiMe3, Me3Si(N3) and Me3SiC=C-Ph have also been studi ed leading to the synthesis of many new organotin(lV) and organotitanium(IV) compounds. The compounds have been characteri sed on the basis of elemental analyses, molar conductances, molecular weights, magnetic susceptibili ties and spectroscopic (lR , lH NM R, UV -vis) data .

IPC Code: Int CI7 C07F 1/08; C07F 3/06 ; C07F 3/08; C07F 7/22; C07F 15/04; C07F 15/06

Currently much interest has been shown on the com­plex ing behaviour of organometallic ligands including fe rrocene-deri ved ligands t

•t6

• A search fo r readily oxidi sable fe rrocenyl ligands has added a further in­centi ve to studies in the field, as the felTi cinium ions possess antitumour acti vity, whereas the parent ferro­cene does not. The acti vity of platinum and go ld complexes 17. 18 of I, l '-bis(di phenylphosphino) ferro­cene (Fdpp) against experimental tumour has been reported. However, Fdpp complexes are not readily oxid ized l9

• The synthesis of oxidi sable fe rrocenyl lig­ands would all ow the design of multifuncti onal drugs . Enhanced anti biotic activity of Penicillin and cepha­losporine has been noted by replac ing aromatic groups with the ferrocenyl mOiet/ D

. It is pertinent to mention here that ferrocene-containing complexes are currently receiving much attention due to their in­creasing role in the rapidLy growing area of materi al

. 7-11i sCIences . Despite ex tensive studies on the metal complexes

of schi ff bases over the past years, the metal com­plexes of fe rrocene containing schi ff bases have not been thoroughly studied. It is onl y recently that some

tpresent Address: Depart ment of Chemistry, Santi pur College, Sant i pur 74 1 404, India

reports on the complexing behaviour of fe lTocene­derived schiff bases have been reported21-24

. There is a possibility that the fe rrocenyl schiff bases and their metal complexes might have redox active properties and also would have applications in non-linear optics and other areas of molecul ar electronics . In view of the multi faceted importance of fe rrocene, fen·ocene­deri ved chelating ligands, and also their metal com­plexes, we have been studying the synthesis and char­acteri zati on of new felTocene-deri ved ligands and also their metal complexess. In continuation of our earlier works, we have recently synthes ized two new thi­azolines by the reactions of I-formylfen·ocene and 1-acetylferrocene with 2-aminoethanethiol, which may remain in equilibrium in so lutions with their corre­sponding schi ff bases (Scheme 1). The reactivities of these thiazolines and the corresponding schi ff bases have never been studied. We, therefore, have studied the reactions of 2-( I-formylfelTocene)-thiazoline (Ffthz) and 2-methyl-2-(l-ferrocene) thi azoline (Mfthz) with M(OAch"nH20 (M = Co, Ni , Cu, Zn , Cd), MCI2·nH20 (M = Cu, Co, Ni), M(N03h"nH20 (M = Cu, Co, Ni), Me2SnCh, MeSnCI3, (1t-CsHsh MCI2 (M = Ti , Zr), (1t-CsHs)TiCI3, (1t-CsHs)TiCh(OMe) and TiCI2(OMeh and in all cases isolated the complexes of the corresponding schiff bases, 2-(1-fo rmyl-

1854 INDIAN J CHEM, SEC A, SEPTEMBER 2004

R = H, Ffthz R = H, HFfimethol

R = Me, Mfthz R = Me, HMfimethol

Scheme I

ferrocene)iminoethanethiol (HFfimethol) and 2-methyl-2-( I-ferrocene)iminoethanethiol (HMfimethol) where the schiff bases acted as monobasic bidentate NS donor ligands.

The reactivity of MeSn(Ffimethol)2Cl and (n­CsHs)Ti(Ffimetholh CI, synthesized in the present in­vestigation, towards MeSH, Me2NSiMe3, Me3Si(N3)2 and Me}SiC=C-Ph is also described in the present investigations.

Materials and Methods

1-Formy I fen'ocene and I-acety I ferrocene (FI uka and Sigma Chemicals) were used as received. These ferrocene derivatives were also synthesized in the laboratory as already reported2s . Other chemicals and solvents used were purified and dried before use by standard procedures. The compounds Me2SnCh and MeSnCI} were prepared following the methods of Luijten and Vander Kirk26 while Me}SiC=C-Ph was prepared as described in literature27

• Di(n­cyc1opentadienyl)titaniumdichloride and di(n-cyclo­pentadieny I)zirconiumdichloride were purchased from Alfa Inorganics. Compounds (n-CsHs)TiCI3, (n­CsHs)TiCI2(OMe) and TiCI2(OMeh were prepared by literature methods28.29.

The elemental analyses were carried out at the RSIC, the Central Drug Research Institute, Lucknow. Some spectroscopic data were also collected from the same centre. The electronic spectra were recorded on Hitachi 200-20 and Shimadzu UV-240IPC spectro­photometers and infrared spectra (KBr/Nujoll hexachlorobutadiene; more than one media were used for some compounds) on a Perkin-Elmer 1330 and LI20-000A FfIR spectrophotometers. The molar conductance was measured using an Elico conductiv­ity bridge. The magnetic susceptibility was deter­mined by the Guoy method. Molecular weights were determined by Rast's method or osmometrically.

Preparation of the ligands 2-(I-formylferrocene)thiazoline (abbreviated to Ffthz) and 2-methyl-2-(I-ferrocene)thiazoline (abbreviated to Mfthz)

I-Formylferrocene (0.214g, 0.001 mol) or 1-acetylferrocene (0.228g, 0.00 I mol) was dissolved in freshly distilled ethanol (70 mL) and the solution cooled to O°e. To this cold solution was then added a solution of 2-aminoethanethiol (0.77 g, 0.001 mol) in ethanol (50 mL) with stirring. A yellow solution was obtained, which was allowed to attain room tempera­ture while stirring. Thereafter, it was stirred for five hours and the volume reduced to half and kept in re­frigerator. The yellow brown compound obtained was filtered off and washed with cold ethanol and recrys­tallized from chloroform-Il-hexane (50:50, v/v) mix­ture to give yellow brown compoun Ffthz and brown Mfthz in about 70 % yield. M.P. of Ffthz 133-136°C(d) and of Mfthz 99-102°C(d).

Preparation of the complexes

The compounds of cobalt, nickel, copper, zinc and cadmium (1 to 10) were prepared by same general method as described below under Nratmosphere:

To a hot solution of Ffthz or Mfthz (0.005 mol) in ethanol (60 mL) was added a solution of M(OAch nH20 (0.0025 mol) (M = Co, Ni, Cu, Zn, Cd) in etha­nol (20 mL) with stirring; a solid compound separated out immediately. However, the reaction mixture was heated under reflux for 2-3 h and compound of the type M(Ffimethol)2 {M = C02

+ (1), Ni2+ (2), Cu2+ (3),

Zn2+ (4) and Cd2

+ (5) or M(Mfimetholh {M = C02+

(6), Ni2+ (7), Cu2+ (8), Zn2

+ (9) and Cd2+ (10) (where

HFfimethol and HMfimethol are schiff base forms of the corresponding thiazoline Ffthz and Mfthz respec­tively) was formed and collected on a filter, washed several times with warm ethanol and dried in vacuo, yield about 65-70 %.

Similar reactions of the thiazoline ligands with MCh'nH20 (M = Co, Ni , Cu) or M(N03)2n-H20 (M = Cu, Co, Ni) yielded analogous complexes as obtained

DEY et al. : SYNTHESIS OF METAL COMPLEXES OF SUBSTITUTED THIAZOLINES 1855

with M(OAchnH20 . When Ffthz and Mfthz were allowed to react with Co(OAch4H20 in access of oxygen, the corresponding cobalt(III) complexes [Co(Ffimetholhl2H20 (11) and [Co(Mfimetholhl H20 (12) were isolated.

To the thiazoline Ffthz (0.682 g, 0.0025 mol) or Mfthz (0.717 g, 0.0025 mol) in methanol­nitromethane mixture (30 mL, 50:50, v/v) was added Me2SnCb (0.275 g, 0.00125 mol) or MeSnCI3 (0.3 g, 0.00125 mol) in dry toluene (40 mL) with stirring. The reaction mixture was stirred for 10 h at -60°C and the solvent removed under reduced pressure. n-Hexane (15 mL) was then added to this crude product and cooled to -lO°C affording [Me2S n(Ffimethol)2] (13), [MeSn(FfimetholhCI] (14), [Me2Sn(Mfimethol)2] (15) and [MeSn(MfimetholhCI] (16) respectively. These were filtered, washed with /1-

hexane and dried ill vacuo, yield 70%.

Similarly, the reaction of Ffthz (0.682 g, 0.0025 mol) or Mfthz (0.717 g, 0.0025 mol) with (n­

CsHsh TiCI2 (0.311 g, 0.00125 mol) or (n-CsHshZrCb (0.365 g, 0.00125 mol) in the presence of stoichiometric amount of Et3N yielded [Ti(FfimetholhCI] (17), [(n-CsHs)Zr(FfimetholhCI] (18), [(n-CsH5)Ti(MfimetholhCI] (19) and [(n­CsHs)Zr(MfimetholhCI] (20).

Analogous reaction of Ffthz (0.273 g, 0.001 mol) in dry chloroform (80 mL) with hot solution of (n-CsHs)TiCI3 (0.109 g, 0.0005 mol), (n­CsHs)TiCI2(OMe) (0.107 g, 0.0005 mol), or TiCI2(OMeh (0.090 g, 0.0005 mol) in dry chloro­form (80 mL) afforded [(n-CsHs)Ti(FfimetholhCI] (17), [(n-CsHs)Ti(Ffimetholh(OMe)] (21) and [Ti(FfimethoIMOMeh] (22).

Reactions of [MeSn(Ffimethol)2CI] (14)

Reaction with MeSH - One equivalent of (14) was added to one equivalent of MeSH in a mixed sol­vent (50:50, v/v) of THF-toluene and stirred at room temperature in the presence of stoichiometric amount of Et3N for 3 days. After removing Et3N.HCI, the vol­ume of the solution was reduced in vacuo yielding the compound [MeSn(FfimethoIMSMe)] (23) on cooling to - lO°C. It was filtered, washed with n-hexane and dried in vacuo, yield 70%.

Reaction with Me2NSiMe3 - As in (23) above, (14) was treated with Me2NSiMe3 in equimolar quan­tities and the compound [MeSn(FfimethoIMNMe2)] (24) was isolated, yield 68%.

Reaction with Me3Si(N3) - The reaction of (14) with Me3Si(N3) in THF similarly gave reddish-brown [MeSn(FfimethoIMN3)] (25), yield 60%.

Reaction with Me3SiC=C-Ph - The reaction of (14) with Me3SiC=C-Ph (l : 1 equivalent) in THF yielded the complex, [MeSn(FfimethoIMC=C-Ph)] (26), yield 55%.

Reaction of [n-CsHs)Ti(FfimetholhCI] (17) -Similarly, the reaction of (17) with MeSH, Me3S i(NMe2), Me3Si(N3) and Me3SiC=C-Ph were carried out leading to the synthesis of [(n-CsHs) Ti(Ffimetholh(SMe)] (27), [(n-CsHs)Ti(Ffimethol)2 (NMe2)] (28), [((n-CsHs)Ti(Ffimetholh(N3)] (29) and [(n-CsHs)Ti(FfimethoIMC=C-Ph)] (30), yield 70%.

Results and Discussion The reaction of I-formylferrocence and I-acetyl­

ferrocene with 2-aminoethanethiol under dinitrogen atmosphere and mild reaction conditions afforded yellow-brown 2-(1-formylferrocene)thiazoline (Ffthz) and brown 2-methyl-2-(l-ferrocene)thiazoline (Mfthz) in good yield. These thiazolines may remain in equilibrium with the corresponding schiff bases 2-(l-formylferrocene)iminoethanethiol (HFfimethol) and 2-(methyl-2-) I-ferrocene)iminoethanethiol (HMfimethol), respectively in solution (Scheme 1). However, in the solid state, the thiazoline structure has been suggested from the infrared and I H NMR spectroscopic data. The thiozolines Ffthz and Mfthz reacted smoothly with M(OAc)z"nH20 (M = Co, Cu, Ni, Zn, Cd), MC\z·H20 (M = Co, Ni, Cu), M(N03hnH20 (M = Co, Ni, Cu), Me2SnCI2, MeSnCI3, (n-CsHshMCI2 (M = Ti, Zr), (n­CsHshTiC13, (n-CsHshTiC\z(OMe) and TiC\z(OMeh in mixed solvents under varied reaction conditions affording new coloured complexes of cobalt(II), co­balt(III) , nickel(II) , copper(II), zinc(II), cadmium(II), organotin(IV), organotitanium(lV), organozirco­nium(IV) and titanium(IV) ions involving the corre­sponding schiff bases HFfimethol and HMfimethol , in their monoanionic bidentate forms as NS donor li­gand. The complexes [MeSn(FfimetholhCI] (14) and [(n-CsHs)2Ti(FfimetholhCI] (17), isolated in this study, reacted with MeSH, Me2NSiMe3, Me3Si(N3) and Me3SiC=C-Ph leading to the formation of thio­lato- , amino-, azido- and ethynylbenzene (or Phen­ylacetelydo) complexes of tin(lV) and titanium(lV) of the type [RM(FfimetholhLd (where R = Me, M = Sn and LI = SMe (23), NMe2 (24), N3 (25), and C=C-Ph (26); and where R = n-CsHs, M = Ti and LI = Sme

1856 INDIAN J CHEM, SEC A, SEPTEMBER 2004

(27), NMe2 (28), N3 (29) and (C=C-Ph (30)]. It may be mentioned here that not many reports are available on the reactions of Me3Si(N3) with "Sn-Cl" bond for the synthesis of azido complexes 18. The isolated metal complexes (1) to (30) are stable at room temperature. The decomposition temperatures of the compounds are recorded in Table I. The azido complex (25) and (29) decomposed with mild explosion at 158-160°C and 156-159°C, respectively.

The newly synthesized compounds have been char­acterized by elemental analyses, molecular weights, molar conductances, magnetic moment values and spectroscopic (UV-vis, IR and IH NMR) data. The characterization data are shown in Table I and the sy nthetic reactions are shown in Figs 1-4.

The molecul ar weights (measured cryoscopically in chloroform and p-dichlorobenzene and also by Rast's method) also support these results. The complexes are so luble in chloroform, nitromethane, DMSO, DMF, pyridine, partially soluble in alcohol, acetone and in­soluble in ether and II-hexane. The molar conductance values of the complexes in DMSO solution (lO,3M) show very low values, in the range 5.8-1 8.0 ohm,Icm2mori (Table 1), indicating their nonelectro­lytic nature30.

All the complexes excepting (1), (3), (6) and (8), are diamagnetic. The cobalt(Il) complexes (1) and (6) exhibit magnetic moments 2.36 8M and 2.39 8M re­spectively at room temperature, which are well in the range of square planar cobalt(ll) species (see elec­tronic spectral discussion). On the other hand, the copper(U) complexes (3) and (8) exhibit magnetic moments 1.79 and 1.78 8M respectively at room temperature, a value close to the spin only value of 1.73 8M, expected for S = 1/2 system. Based on these magnetic moment values, either a di storted octahedral or a sq uare planar geometry may be proposed for these copper(Il) complexes (3) and (8)31 in the solid state (see electronic spectral data).

The square planar geometry for the cobalt(lI) com­plexes (1) and (6) (Table I) is further substantiated by the electronic spectral data (in nitromethane) of these two complexes showing bands in the region 560-555 and 450-425 nm regions attributable to 28 2g ~ 4Eg(P) and 282£ ~ 4A2g transition32 (D4h sy mmetry). The cop­per(lT) complexes (3) and (8) display two or three bands in the visible region, the bands at 7~0-750 nm being assigned to 281g ~ 2AI g and 28 1& ~ 282g transi­tions, while the second band at -500 nm can be at­tributed to 281g ~ 2Eg transition, commensurate with a

distorted octahedral structure33. The diamagnetic co­balt(III) complexes (11) and (12) show two broad bands at around 670 and 470 nm regions, which may tentatively be assigned as the split components of the IA IT . . d IA IT .. 1£ ~ 1£ transition an to Ig ~ 2£ transition obscured by the ligand Tt-Tt* transitions34 . This sug­gests a pseudo-octahedral structure for the complexes (11) and (12). The diamagnetic nickel (II) complexes (2) and (7) are probably square planar. This observa­tion is supported by the electronic spectral bands in the 720-680 nm and 480 nm regions, assignable to IA IA d IA 18 ... Ig ~ 2£ an Ig ~ Ie trans1110nS 111 a square planar field around nickel(lI)JS,36.

The UV-spectral bands of the thi azoline ligands Ffthz and M fthz and the complexes were measured in chloroform. The absorption bands at about 260-270 nm may be due to B band of the cyclopentadienyl ri ng37. The d-d transition might infl uence these bands as reported earlier37

. A high energy band around 350-330 nm may be assigned to the M-L charge-transfer band. This band was found to shift by about 5-15 nm to a higher wavelength38. The band around 460-475 nm is almost close to that in the free ligand39.

The IR spectra of the thiazolines Ffthz and Mfthz show band at -3250 cm-I (medium) assignable to VN-H. On the other hand, the free thi azolines show no bands around 2570-2590 cm- I and 1600-1625 cm- I

assignable to VSH and VC=N respecti vely. These obser­vations suggest that in the solid state the ligand re­main in thiazoline fonn40 (Scheme I). However, in solution, both the thiazoline and the corresponding schiff base may remain in equilibrium36.41 (Scheme I). The characteristic bands of the ferrocene group appear at 3080,1445,880 and 515 cm-I (ref. 42). Tn the com­plexes (1) to (30), the VN-H band disappears and a new band due to azomethine group (>C=N) is observed at around 1610-1620 cm-I, which may be considered as coordinated azomethine group. This also supports the fact that the thiazoline ring in the presence of metal ions, rearranges to its schiff base form and finally acts as a monobasic bidentate NS donor ligand in the complexes (Table 1). The Vc-s mode of the ligands around 770-730 cm-I is shifted to around 720-700 cm­I in the metal complexes indicating an M-S linkage. This is further substantiated by appearances of new bands in the region 360-320 cm- I in the metal com­plexes which are ass ignable to VM-S (M = metal ions)43. The appearances of bands in the region 555-500 cm-I in the complexes are additional support of N and 0 linkage to the metal atom41 . A medium intense

Table 1 - Characterization data of the complexes

Compound Colour M.P. Mol.Wt Found (Calcd.), % ~efr' AMb

(0C) Found C H N CI M B.M. rr l cm2

(Calcd.) mor l

HFfimethol Yellow- 136-138 (d) 258 57.80 5.76 5.02 C J3H lsNSFe brown (272.97) (57.15) (5.54) (5.12) 0

tTl HMfimethol Brown 102-105 (d) 271 58.78 5.78 4.99 -< C I4H 17NSFe (286.98) (58.54) (5.97) (4.87) ~

'" :-[Co(Ffimethol) 21 (1) Brownish 158-162 (d) 590 51.66 4.28 4.00 9.29 2.36 5.8

C/J C26H28N 2S2Fe2Co -yellow (602.85) (51.75) (4.68) (4.64) (9.77) -< z [Ni(Ffimetholh1 (2) Reddish- 142-145 (d) 630 51.58 4.78 4.29 9.22 dia 8.9 -l

:r: C26H28N2S2Fe2Ni brown (602.63) (51.77) (4.68) (4.64) (9.74) tTl

C/J

[Cu(Ffimethol)21 (3) Light- 154-157 (d) 596 51.49 4.88 4.72 10.66 1.79 10.11 C/J

C26H28N2S2Fe2Cu brown (607.42) (51.36) (4.64) (4.61) ( 10.45) 0 "r1

[Zn(Ffimethol)21 (4) Light- 162-165 (d) 620 51.78 4.28 4.99 10.72 dia 15.2 3::: tTl

C26H28N 2S2Fe2Zn Yellow (609.22) (51.21) (4.63) (4.59) (10.72) -l >-

[Cd(Ffimetholh1 (5) Light- 162-166 (d) 642 47.60 4.36 4.45 17.25 dia 16.8 r n

C26H28N2S2Fe2Cd Brown (656.32) (47.53) (4.23) (4.26) (17.12) 0 3:::

[Co(Mfimetholh1 (6) Yellowish 114-117 (d) 658 . 53.48 5.28 4.92 9.57 2.39 15.5 "tl r C28H32N2S2Fe2Co -brown (630.87) (53.26) (5 .11) (4.44) (9.34) tTl

>< [Ni(Mfimetholh1 (7) Red 115-120 (d) 53.71 5.67 4.80 9.70 dia 12.5

tTl C/J

C28Hl2N2S2Fe2Ni (630.65) (53 .28) (5.11) (4.44) (9.31 ) 0 "r1

[Cu(Mfimetholh1 (8) Brown 116-120 (d) 52.98 5.28 4.88 10.01 1.78 10.8 C/J c:

C2sH32N2S2Fe2Cu (635.44) (52.87) (5.07) (4.40) (9.99) 0::1 C/J

[Zn(Mfimethol) 21 (9) Light- 120-124 (d) 52.26 5.89 4.78 10.82 dia 9.2 -l =i

C28HnN2S2Fe2Zn yellow (637.24) (52.72) (5.60) (4.39) (10.25) c: -l

[Cd(Mfimethol)21 (10) Light- 119-122 (d) 49.11 4.92 4.12 16.80 dia 10.8 tTl 0

C28H32N2S2Fe2Cd brown (684.34) (49.09) (4.71) (4.09) (16.42) -l :r:

[Co(Ffimetholh1 (11) Brown 174-178 (d) 860 53.68 4.99 4.72 6.55 dia 18.0 :; C39H42N3SlFelCo (874.81) (53.49) (4.84) (4.80) (6.73) N

0 r

[Co(Mfimetholh1 (12) Brown 142-144 (d) 54.88 5.38 4.90 6.80 dia 11.0 Z C42~sNlSlFelCo (916.84) (54.97) (5.27) (4.58) (6.42) tTl

C/J

[Me2Sn(Ffimetholh1 (13) Reddish- 140-143 (d) 720 48.80 4.85 4.11 17.91 dia 6.8 C2sH34N2S2Fe2Sn brown (692 .66) (48.50) (4.95) (4.04) ( 17.13)

[MeSnCI(Ffimetholh1 (14) Brown 144-147 (d) 689 45.68 4.28 3.37 4.80 16.77 dia 9.7 C27HJIN2S2Fe2SnCI (713.14) (45.43) (4.38) (3.93) (4.97) (16.64)

(Conlel) 00 Vl -.J

00 Vl 00 ----------

Table 1 - Characterization data of the complexe!-Contd

Compound Colour M.P. Mol.Wt Found (Caled.), % IJ..:rr' AMb

(0C) Found C H N CI M B.M. Q .lcm2

(Caled.) mol'l

[Me2Sn(Mfimelholh] (15) Brown 146-148 (d) 49.88 5.60 3.90 16.85 dia 8.8 C)OHJsN2S2Fe2Sn (720.7) (49.95) (5.31) (3.88) (16.47)

lMeSnCI(Mfimetholh] (16) Brown 147-151 (d) 47.00 4.88 3.57 4.98 16.55 dia 15.8 C29HJsN2S2Fc2SnCI (741.18) (46.95) (4.76) (3.77) (4.79) (16.01)

[(1t-CsHs)Ti(FfimclholhCI] (17) Yellow- 152-155 (d) 715 53.53 4.68 4.28 5.80 6.77 dia 12.2 CJIHJJN2S2Fe2TiCi brown (692.36) (53.73) (4.80) (4.04) (5.12) (6.92)

[(1t-CsHs)Zr(Ffimcthol)2CI] (18) Brown 154-158 (d) 50.79 4.22 3.68 4.90 12 .. 80 dia 5.0 CJIHJ3N2S2Fc2ZrCi (735.68) (50.56) (4.52) (3.80) (4.82) (12.34) Z

Q [(1l-CsHs)Ti(MfimetholhCI ] (19) Reddish- 150-155 (d) 54.88 5.72 3.68 4.78 6.66 dia 6.8 >-

C33H37N2S2Fe2TiCI brown (720.39) (54.97) (5.17) (3.88) (4.92) (6.65) Z ......

[(1t-CsHs)Zr(Mfimethol)2C1 ] (20) Reddish- 150-154 (d) 51.88 4.99 3.82 4.92 11 .67 dia 13.0 () ::r:

CJJHJ7N2S2Fe2ZrCi brown (763.71) (51 .85) (4.88) (3.66) (4.64) (11.94) tTl s::

[(1t-CsHs)Ti(Ffimetholh(OMe)] (21) Brown 152-156 (d) 670 55.62 5.80 4.42 6.76 dia 19.0 (/l

C32H3~2S2Fe202Ti (687.88) (55.82) (5.27) (4.07) (6.96) tTl ()

[Ti(Ffimetholh(OMeh] (22) Yellow- 154-159 (d) 51.58 5.99 4.68 7.50 dia 12.8 ? C2sH)4N2S2Fe202 Ti brown (653.87) (51 .38) (5.24) (4.28) (7.32) (/l

tT1 [MeSn(Ffimetholl2(SMe)] (23) Brown 162-166 (d) 700 46.82 4.90 3.62 16.80 dia 10.9 ~ CzsH)4N2S3Fe2Sn (724.67) (46.36) (4.72) (3.86) (16.38) tTl

s:: [McSn(Ffimetholl2(NMez)] (24) Brown 172-177 (d) 48.60 5.82 5.60 16.20 dia 9.0 c:l

tTl C29H37N3S2Fe2Sn (721.69) (48.22) (5.16) (5.82) (16.44) ;:0

N

lMeSn(Ffimetholh(NJ)] (25) Reddish- 160-165 (d) 45.28 4.59 9.99 16.89 dia 12.2 0 0

C27HJINsS2Fe2Sn brown (719.64) (45.02) (4.34) (9.72) (16.49) .j>.

[MeSn(Ffimetholh(C-=C-Ph)] (26) Brown 152-155 (d) 53.28 4.50 3.90 15.80 dia 15.0 CJSH~2S2Fe2Sn (778.68) (53.93) (4.66) (3.59) (15.24)

[(1l-CsHs)Ti(Ffimetholh(SMe)] (27) Yellow- 154-157 (d) 688 50.44 5.88 13.04 12.88 4.85 6.0 C32HJ~2SJFc2Ti brown (703.88) (50.12) (5.61) (12.99) ( 12.74)

[(1t-CsHs)Ti(Ffimetholh(NMe2)] (28) Brown 160-164 (d) 56.80 5.72 5.78 6.88 dia 10.9 C33HJ~3S2Fe2Ti (700.91) (56.49) (5 .60) (5.99) (6.83)

[(1t-C5Hs)Ti(Pfimetholh(NJ)] (29) Brown 156-60 (d) 53.68 4.98 10.29 6.66 dia 16.2 CJIH31NsS2Fe2Ti (698.86) (53.22) (4.76) (10.01) (6.85)

[(1l-CsHs)Ti(Ffmctholh(C~-Ph)] (30) Brown 162-165 (d) 61.88 5.82 3.89 6.62 dia 18.0 CJ9HJsN2S2Fe2Ti (757.9) (61.75) (5.05) (3.69) (6.32)

a) Solid state at room temperature. b) 10· 3 M solution in DMSO at room temperature

DEY et al. : SYNTHESIS OF METAL COMPLEXES OF SUBSTITUTED THIAZOLINES

M(OAc)2 nHp, EtOH

/ R = H, Ffthz R = Me, Mfthz

4H 0, EtOH

..

R = H, M = Co2+(1) R = H, M = Ni 2+ (2) R = H, M = Cu 2+ (3) R = H, M = Zn2+ (4) R = H, M = Cd2+ (5) R = Me, M = Co2+(6) R = Me, M = Ni2+ (7) R = Me, M = Cu2+ (8) R = Me, M = Zn2+ (9) R = Me, M = Cd2+ (10)

R = H , C0 3+ (11) R = Me, Co3+ (12)

Fi g. I - Reactions of Ffthz and Mfthz with metal acetates and probable structures of the isolated complexes

f .

M',S,CI"M,OH- M,NO, ~y\ Me-4~ • Fe /

~ N, @LT1 ~J R = H, (13) & R = Me, (15)

~ R ~ H, Ffthz ~ r-'\ ~

R' M~fth' ~Fe ~/~ M'-4 "" MeSnCI), MeOH - MeN02 "\

~-N-2 ----@LT1

R= H,(14) & R= Me,(16)

Fig. 2 - Reactions of Ffthz and Mfthz with organotin(lY) compounds and probable structures of the compounds

1859

1860

R = H,Ffthz R=Me,Mfthz

INDlAN J C HEM , SEC A, SEPTEMBER 2004

MeOH - MeN02 - CHCI3

N2

.. . ;4J~7

R = H,M= Ii (17) R = H, M "" Zr (18)

-R = Me, M = Ii (19) R = Me, M = Zr (20)

l' = 1t-C5Hs, L = CI (17)

l' = 1t-C5Hs, L = OMe (21) 1'= L = OMe (22)

Fig. 3 - Reactions o f Ffthz and Mfthz with organotitanium(IV) chlo rides and chloro-alkoxides and probable struc tures of the isolated complexes

R = Me, M = Sn (14)

R = 1t-C5H5, M = Ti (17)

MeSH

THF-PhMe,Et,N

THF-PhMe

M~SiC=C-Ph

THF-PhMe

R = Me, M = Sn, L = SMe (23) R = Me,M = Sn,L =NMe2 (:~4)

R = Me, M = So, L = N) (2~i)

R = 1t-C5H5' M = Sn, L = C=C- Ph (26)

R = 1t-C5H5, M = Ti, L = SMc: (27)

R = 1t-C5H5, M = Ti, L = NMc:zI)8)

R = 1t-C5H5, M = Ti, L = N) (29)

R = 1t-C5H5, M = Ti , L = C=C- Ph (30)

Fig. 4 - Reac tions o f [MeS n(FfimctholhC lj (14) and [1t-C5H5)Ti(Ffilllctho l)2C lj (17) w ith McSH, Me1NS iM e.h Me3S i(NJ) and Me3SiC=C-Ph and probable structure o f the isolated complexes

DEY et al. : SYNTHES IS O F M ETAL COMPLEXES OF SUBSTITUTED THIAZOLlN ES 1861

band observed at about 335 cm-I for the complexes

(14) and (16) may be ass igned to VSn_C144

. The pres­ence of Ti-CI bond in the complexes (17) and (19) and Zr-CI bond in the complexes (18) and (20) has been inferred from the appearance of bands in the in­frared spectra of the complexes in the region 290-300

-I cm . The IH NMR spectra of Ffthz and Mfthz in CDCI3

and some of the complexes in CDCI3 and DMSO-d6

were measured which support the conclusion deri ved

above. The N-H proton signals of the thi azolines at 8 11 .9-1 2.2 ppm di sappeared on dueteration. The two

thiazolines exhibited two peaks at 8 4.2 (s) and 4.8 (br), ass igned to proton signals of unsubstituted and substituted cyc lopentadinyl rings of the ferrocene moiet/ 5

, respecti ve ly. Signal for the NH proton as mentioned above, al so disappeared in the compl exes. Thi s indicates the complexation of the thi azo lines in the schiff base forms, whi ch fun ction as bidentate monobas ic NS donor ligands. Thi s is in line with the conclusion drawn from magnetic and spectroscopi c data (di scussed above). The thi azo line Mfthz di s­played an additi onal signal at 8 2.2 1 (s) which may be

taken as the presence o f >C- CHJ groupl S. In the com­plexes (DMSO-d6) there is no appreci able change in the chemi cal shi fts o f fe rroceryl protons on che­latronl8. Correct integrati ons are consistent with the fo rmulae (Tabl e 1). The sharp signals fo r S-CH3,

N(CH3h Sn(CHJ) and Sn(CHJh protons at 8 3.2, 3.4, 0.95 ppm and 8 ].1 ppm respecti vely in the com­pl exes (13) to (30) suggest the trans arrangement of these ligands. The signals for the methylene protons in the free thiazolines and also in the complexes may

appear as multiplet in the region 8 2.9 to 8 4.2 ppm and mi x up w ith the signals of other groups men­tioned above. On the bas is of the above di scuss ion, the structure of the isolated complexes may tenta­ti vely be proposed as depi cted in Fi gs 1-4.

Acknowledgement The authors are than kful to the Regional Sophi sti ­

cated Instrumentation Centre, the Central Drug Re­search Institute, Lucknow, fo r elemental analyses and spectroscopic data. One of the authors (SS) is grateful to the University of Kalyani for a Junior Research Fellowship. Fac ilities provided by DST-FIST are gratefull y acknowledged .

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