g ELSEVIER Inorganica Cimi Aet 2711998) 83.92 Synthesis, spectroscopic and electrochemical study of nickel(II) complexes with tetradentate asymmetric Schiff bases derived from salicylaldehyde and methyl-2-amino-1-cyclopentenedithiocarboxylate Eulalia Pereira, Ligia Gomes, Baltazar de Castro * CHOU Facade de Cn Resi 22 May 197; ase § Abt 197 Abstract [New teradenate ligands with NOS coorintion sptes were prepa und the corresponding nickel(I)complenes were synthesized and characterized by analytical, spectroscopic ard electrochemical methods, The acta of nickel methy-2-[N-[2-(¥ -methony- hen ‘late mthylidynenito ety! |aminato-1)1-eyclapentenedthiccarboxylac} has been detemined by X-ray crystallography. Thiscomex rytlizes inthe ontborbombic space group 72,2,2 with a= 11-417 (3), b= 18889 (4), e= 12.769 (3). = and Ry =11.0539 fr 4641 teflections with > 2a J), The UV-Vis and'H NMR spectroscopic ests neat thatthe complexes have 3 square planar strut i the ‘li state ain 0 ‘athe ign tenon tn. Electochemcal and EPR dat show tit he complexes ae reduced to he correspondent sicko) compleses but cent in the electrochemicl oxidation ofthe complees, 1 1998 Elesier Science S.A Kemwonde Cyt scr Ehcohemry; Nikl corpones Sci hse cores 1. Introduction “There is currenly a reat interest inthe study ofthe factors that influence the accessibility of several oxidation states for ickel, specially related othe bio-inorganic role of thismetal fon in several redox enzymes [1]. Elucidation of the funda mental stractural and electronic factors that influence the relative stability of several oxidation states ofthe metal may ‘be useful in understanding the enzyme reactivity and inthe ‘optimization of the design of model compounds. Further imerestin the coordination chemistry of nickel 1) arises from the role ofthese complexes in several catalytic reactions, such as electrocatalstical (2] and phorocaalytical (3] reduction ‘of COs, and electrcataltial reduction of alkyl halides (4). Ir has been suggested thatthe incoeporstin of both soft and hard donors the coordination environment ofthe metal ‘on may be erica in the stabilization of oxidation numbers “1 and +3 for nickel [5]. This hypothesis, in conjunction with experimental evidence thatthe coordination environ- tment of nickel in NiFe hydrogenases [6] and CO-dehydro- genase (7 contains sulphur, nitrogen and/or oxygen donors. resulted in a continuing effort to obtain nickel complexes, “Comespoeding author. TeL: +381 2 608 28 92, Fax: +351 2.608 29, So Boma bentotte snp 70-16198/S1900© 198 vier Science S.A. All gts served Pu'so020- 1695195039088 \with this kindof coordination environment. We have synthe sized and studied the nickel(l) complexes depicted in ‘Scheme 1, which possess a mixed N,OS coordination sphere The comesponding symmetric nickel complexes with igands derived from salicylaldehyde, [Ni(salen) |. and methyl-2 amino-I-eyclopentenedithicarboxylate, [Ni(edzen)] have been studied by others [8.9], and the results may be com- pared with those obtained in the present work in order to ‘verify if there are some synergic effets between the 180 halves of the igand, which may be responsible for additional accessibility of multiple oxidation states for nickel 2. Experimental 2.1, Materials All solvents used in the preparations were reagent grade ‘Chemicals forthe preparations were reagent grade and com- ‘mercially available, and were used without further puritica- tion, The eletrochemical measurements were performed in [N.N’-dimethylformamide (df) (Merck, proanalisi tetra butylammoniuin perchlorate (TBAP) was prepared by pub- lished methods {10}. CAUTION: perchloratesarehazarous and may explode,u Perea al./ Inorganica Chimie Act 271 1998) ee eG AAS \ aaa a esgon Meade) CH, SH RR (seston Hon [NicdMeslen! = CH, INiciMeoatey) =H 3.0 MiledMeOrgalen}] HM 464CH,0), [(eaMeMeOsslen)) CH, SCH, (NieéChsaleny =H asc, R (engpen " [ieaenapen} cit, eae NZ as Dvisen) 2.2. Instrumentation Elemental analyses (C; Hand N) were performed atthe Micro Analytical Laboratory, University of Manchester and. atthe Departamento de Quimica da Faculdade de Ciencias doPorto. UV/Vis/NIR spectra were recorded ona Shimadzu LUV-BIOIPC spectrometer, NMR spectia ona Bruker AC200 ‘or a Briker AMX300 spectrometer in deuterockloroform. unless otherwise stated, with tetramethylsilane as interal standard Electrochemical measurements were nade witha PAR 362 ‘using solutions = 110°" mol dm” in complex and 0.1 mol dm”? in TRAP. Cyelic voltammetry was performed in ‘dmfusingathree-electrode eel, with platinum microsphere as working electrode, platinum fil ascounterelectrode and dan Ag/AgCl (I mol dm”? NaCl) reference electrode. nal. cases, ferrocene (Fe) was used as an under the experimental conditions employed Fe couple is 485 mV. All potentials are reported relative to ‘Ag/AgCl (1 mol dm”? NaC), Controlled potential electrolysis of the nickel(I1) com plexes was performed using strictly ancerobic eantions in 8 thtee-clectrode cell, with a platinum gauze working cle teode,a platinum foil counter electrode and an Ag/ AgC! (1 ‘mol dm" NaCl) reference electrode. The potemial applied was approximately $0 mV more negative than the cathodi ak potential determined inthe votfammesi experiment. [EPR spectra were obtained witha Bruker ESP 300E spee- trometer (9 GHz) in « dual cavity, using dipheny picryl hydrazyl (dpph; ¢=2.0037) as an external standard: the magnetic fed was ealbrated by use of Mn in MgO, Spec> tea were obtained at 77 K, using sealed quartz tubes, 2.3. Somtesis ‘Methyl-2-1N-(2"-aminoethane -amino- -eyelopentene lithiocarboxglate (Heden) was prepared by published methods (11,12) 2.3.1. General procedure forthe synthesis ofthe ligands Alle ligands used in his work were prepared by addition ofthe equimolar amount ofthe appropriate salieylaldehyde 10 a methanolic solution of Heden. The yellow products obtained were rerystalized from methanol-ctloroform, 1: val. 23I-L. Methyt-2-(N(2(2'-ydraxyphenslimethylidyne- nitrilojeths!}amino-L-eyclopentenedithiocarbarslate, Hacdsalen "Yield 79.85. Aga( dnt) /nmn 314 (loge nu, 415) and 398 (4.36): By (200 NB CDC) 1.82 (2 Hom), 259 3H, 8).2.65-2.79 (4H, m), 3.72 (2 H.1), 385 (2 H. 0), 664 697 (2H, m), 723-7.36 (2H, m), 840 (1 Hs, CH=N), 12,38 (1H, bes, NH) and 12.88 (1 H, br s, OH) (Pound:C, $9.4; H, 6.27; N, 855; S, 200%. C\cHpNOS, requires C, 60.0; 1.6.29: N, 8.74: 5, 200%) 2.31.2. Methyl-2-(N[2(2'-ydroxyphenslethylidyne- hiro Jesh! )amino-I-eyclopentenedithiocarbosylate, HcdMesalen Yield 634%. Ayas(dimf) fam 313 (loge 4.12) and 398 (4.36); By (300 Mz; CDCI.) 1.85 (2 Heim), 236 3H. 5}, 258 (3H, 8),2.73 (2 H.0),2.79 (2 Hy1),3:76-385 (4 Hm), 682 (1H. 0), 694 (1 Hd), 730 (1,0, 753 (1 Hid). 12.45 (1H. br s, NH) and 154 (1H. bs, OF) (Found: C, 0.0; H, 658; N, 8.28: $, 19.69:. C,HaN;OS, requires C, 61.0; H, 6.63: N, 8.37: S, 19.25) 21.3. Methyl-2-(N-[2.(2"Iydroxy-3!-methoxyphens!)- Imethslidynentrilo ety! jamino-I-eyclopenteneditio carboxylate, HyedMeOsalen Yield 78.4%. Agua( df) /am 313 (loge, 411) and 398 (4.38): dy (200 Miz; CDC) 1.80 (2 Hm), 2.56 3 H, $).2064-2.77 (4H, mm), 3.75 (2 H,), 386 (2.2), 3.90 (3 Hs, OCH,), 679-697 (3H, m), 839 (I H, s, CHEN). 12.36 (1H. brs, NH) and 13.27 (1H, brs, OH) (ound: 57.9; H, 6.17, N, 816: 8. 18.3%, CoHN,O.S; requires (C1582; H, 6.33: N. 7.99; 5. 1834), 23.14, Methy-2-(N[242'ydroxy-5"-merhylphenl)- etlidynenitrio ets!) amino: I-evelo-pentenedithio carboxslae, Hedi salen Yield 63.8%. Apas(dmf) nm 315 (logénus 415) and 398 (4.40); 5, (200 MHz; CDCI,) 1.84 (2 Hy), 2.29 (3 Hs), 233 3 Hs), 257 GH. s), 268-282 (4 H, m), 3.78-382 (4H, 1m), 683 (1H. d), 7.10 (1 Hd), 7.30.1 Hs), 1244 (1H, bes, NH) and 15.16 (1H, brs, OH) (Pound: C. 62.0; H, 698: N, 807; S, 18.2%. C,HayN,0S, requires C. 62.0:H, 694: N. 804; S, 184%) 23S, Meths-2-(N-[2-2'-hydroxy-4'.6'stimethoxy: hens! methsidsneniofethy!\amino-I-cyclopentene: Uithiocarborslate, Hed! MeO) salen Yield 62.89%. Ayaa(dmf}/m 289 (sh>, 312 (loge. 4.38) and 398 (4.39); 8 (200 MHz: CDCI) 181 2H. 1m), 257 (3,8), 262-279 (4H, m).3.47-3.73 (4m), 377 3H. s, OCH), 2.78 (3 H, 5, OCH,). 5.76 (1 H, d) 5.98 (1 Hd), 854 (1 H,s, CH=N), 12.38 (1H, brs, NH) land 14.18 (1 H, bes, OH) (Found: C, $6.5: H, 639: 7.43; 5, 16.1%. CHauN:038> requites C, 6.8; H, 6.36: N, 7.36; 8.169%). 2.3.16, Methyl 2-[N2(2'-ydraxy.5!-methoxyphen)- ‘tiyldyentrilofnhs!amino-I-celopentenedithio carboxylate, HscdMeMeOsalen Yiekd 777%. byo(denf)/nmm 289 (sh). 313 (lozene, 4.05) and 397 (4.37); 6y (200 MHz; CDCI,) 1.84 (2H, 1m), 233 (3 H,s),257 GH, ),269-2.83 (4 Hm), 374 3,87 (7 Hom, CH and OCH), 685-6.96 (2 Hm) 7.04 Hd}, 1245 (1 HL br s, NH) and 14.77 (1 HL, brs, OF) (Found: C, 58.7; H, 665; N, 753: 8, 17.6%. CygHa.N,O8: requires C, 59.3, 6.64; N. 7.68; S, 17.6%). 231.7. Methl-2-(N242'S'-dichloro-2-hydroxy- henvl)meshlidynenitrio ety! amino-1-eyclopentene: ditiocarboxvtate. H-cdClsalen YVield 98.0%. Aya df) am 314 (loge ny, 4.08) and 397 (4.30): By (200 Miz: CDCI.) 1.83 (2 Him), 2.58 (3 H. 5), 263-279 (4H, m),375 (2H.1),388(2H,0,7.17 (1 Hs) 741 (1 H,s),8.33 (1,5, CHAN), 12.28 (1H, bes, NH) and 13.85 (1 H, brs, OF) (Found: C. 49.6: H, 4.53, N, 7.34; §, 166; CL. 18.4%, Cy(CLHysN2OS, requires C, 49.4: 4.66, N, 7.202, 16.5: Cl, 182%). 2.31.8. Methyl-2-[N-[2(2'-hydrasynaphahjmedhslidne: iro eth! amino I-eyelopentene dithiocarboxslate, Heednapen Yield 71.0%. Apea(dmf)/am 313 (ogenay 427). 398 (437) and 420 (sh) 6, (200 MHz; CDCI) 1.72.(2 Hm), 254 (3H, s),2.56-2.66 (4 H,m),3.72-3.86 (4H. m). 6.99 (LHL 4) 7.26 (1H, 0), 742 (1 Hh 2), 7.63-7.76 (2 Hm), 7.87 (1H), 1249 (1H, brs, NH) and 14.56 (1H, brs. OH) (Found: C, 642: H, 594: N, 7.51; S, 172%. ‘CoyH NOS; roquites C. 648: H, 5.98; N, 7513 8.173%), 2.3.1.9, Methyl-2-\N-[2-(2"ydraxynaphihslethslidyne hitrlo eth! annino-I-cyclopentenedithiocarbaxylate, HocdMenapen Yield 77.34. Agaa(dme) am 313 (logenas 405), 338 (sh) and 400 (4.02); 6, (200 MHz; CDCI,) 1.76 (2H. 2.56 (3 H.s).2.60 (3 H, 5), 2.68-2.78 (4 H, m), 380-385, (2B, m), 701 (1H, d) 7.26 (1 H.0).7.40 (1H, 0), 7.60— 7.69 (3 Hm) and 12.53 (1 HL bes, NH) (Found: C, 613: H, 638; N, 7.05; S, 16.4%, C.\Hy.N.OS; requires C, 65.6 H.6.29:N, 7.28: 8. 16.7%) 23.2. General procedure for nickel) complexes ‘To a solution ofthe appropriate ligand (0.1 mmol) in 10 cm’ of chloroform /methanol 2: vol/vol, was added asolu- tion of nickel acetate tetrahydrate (0.25 2, 0.1 mmol) in 10 cm of methanol. The solution was stirred for 15 min and then allowed to stand at room temperature for 24 b. The resulting green or brown powder was recrystallized from scetontile/methanol 1:1 vol/vol 2.3.2.1, Mikellmethyl-2-(N-[2-(2"-phenolate)- ‘methslidynenirlo eth} aminato-1)-I-eyclopentene dikiocarborstat. [Nifedsalen)] ‘Yield 99.85. 6, (200 MHz; CDC) 1.82 (2 H, m), 248 (2,1), 262 2H,0,267 3H, 9), 326 (2H.0).333 (2 H,0, 649 (1 H,0),6.79 (1 Hd), 707.13 (2 Hm) and 1188 (1 His, CH-N) (Found: C, 50.5; H, 547: N, 7486 CyHNsOS.Ni requires C, SLO: H, $.35;N, 743%.6 Peri Iori Chin Ata 271 988) 8-92 2.3.2.2. Nickell methyl-2-(N-[2-(2' phenolateethslidene- irda jet!) aminatt-1)-L-eyelopemtenedithiocarboxvlate, INi(cdMesalen)} Yield 41.8%. 6, (200 MHz; CDCI,) 1.84 (2 H,m),2.44 (3 Hs), 249 (2H, 0, 262 (2,0), 268 (3 H,5).322 2 H.0,355 (2H,0.652 (1 H,0.685 (1 H.d).7.10 (1H 1) and 7.49 (1H, €) (Found: C. $2.1: H, $01; N, 7.20% (CyHyN,OS,Ni requires, $22; 1.5.18; N. 7.16%) 23.2.4, Mikellmethyt-2-(N12-(3"-methory-2 henofate me sidyneninrio ess! }aninatot-1)-T-eyelo= pentenedihiocarboxylate, (Ni(edMeOsalen)] Yield 78.4%. 6, (200 MHz; CDC) 1.85 (2H.m), 251 (21,1), 264 (2,0, 269 GH, 8), 323 (2H.0),353 (2 H,0), 375 (OH, s OCH,), 6444 (1H, 0), 665-678 (2 H, mm) and 7.77 (1 H, s. CH-=N) (Found: C. 49.9; H, 5.00; 674: 8, 15.5%. CHayN2O28:Ni requires C, 50.2: 5.45: N,6.88:5, 157%) 2.3.24, Nikel{methyt-2{N1245' metiyt2 Phenolateerylidsneniril ett amenatt-1- Ive pentenedihiocarborsate,[NiedMessalen)] ‘Yield 63.8%. 8, (200 MHz: CDCL) 181 (2H ).220 (31 8),240 GH ),245 (2H, 2.61 (2H) 2673 H,5).823 2H. 356 21.0.6.3 (1H. d).692 (1H, and 715 (1 H.s) (Found: C, 583: 1H, S47: N, 676. 8, 15.6%, CyHNO8.Ni requires C, 514: H.S97.N, 691, 8.158%) 23.25, Nickell methyh-2-(N12-(4'6'-dimethors-2"- henolate methstidsnenitrio ery! aminatof)-Tneyeo pentenedithiocarboxslate, (NiledtMeO)-salen)} Yield 62.8%. 6, (200 MHz; CDCI) 1.84 (2 H.m), 25 (21,0, 264 (2,0, 268 3H, s)-320(2H,0,34702 H.),3.71 GH, s,OCH,). 3.76 (3, OCH). 5.61 (1H, 5)+5.96 (1 H,s) and 8.10 (1 H.s, CH=N) (Found: C494 H.4.95:N,628:S, 15.0%, CgHsN,O,8,NicequiresC,49 5; H.SOT.N. 631: 5, 147%) 2.5.2.6, Nickel{ methyL2-(N-[2-(3"-methoxy-2 henolatejethslidynenitriloethy!)amirato-1)I-eyelo pentenedithiocarboxslate (NiedMeMeOsalen)] Yield 77.7%, 5y (200 MHz; CDCI, 84 (2H, m).241 (BHLS).244 (21.0, 263 (2.0), 2.67 (3 Hy), 3202 H,0, 352 (2 H.0),373 (HL s, OCH) and 6 80-686 (3 H. m) (Found: C, 509; H, $30, N, 646; S, 15.2%. ChblssNsO.8:Ni requires C, $13; H,'S.74: N, 665; S, 152%), 2.4.2.7, Nickell methyl-2-(N-[2-(3'8'-dichloro-2 ‘phenolateynethsliynentrilo ethyl aminatot-1)-Leyelo- ppentenedithiocarboxslate, (NifedClsaten}] Yield 98.0%. 8, (300 MHz; CDCI) 1.84 (2H,m),2.55 269 (4 Hy m), 2.63 (3 H, s}, 333 (2H, 0). 267 (2H. 7.40 (1H, 8), 743 (1 HL 8) and 828 (1H, s, CHEN) (Found: C, 42.9: H, 299: N, 6.15: 1N.OS;CLNi requires 43.1: H, 407; 14.2%, Cube 1628; S. 14.45) 22.28, Nickel{methyl-2-[N-[242'-naphiholate)- ‘methylidyneniriloethy!aminatoy-1)-T-esclopentene- diutiocarboxstate {Nifcdnapen)] Yield 71.0%, 6, (200 Miz; CDCI) 1.84 (2 H.m), 2.81 (2H), 264 (2.0, 2.69 GH, 8).326 (211). 265 2 H.0),698 (1 M.d). 724 (1 H,0), 740 (1 H,0), 752-763 (2H, m), 784 (1H, d) and 857 (1H, s, CH=N) (Found: ©, 55.9:H,5.68:N, 6,36:5, 15.3%, CHyyNOS,Nirequies (©, 36.2; H, 598: N, 6.56: 8, 150%) 2.3.29. Nickel{methy-2-(N-(242'-naphtholate> ‘ethsldynentril ey! aminatot-)-Icyelopentene: dithiocarboxslate,[Ni(cdMenapen)] Yield 7735. By (200 MHz; CDCI) 1.83 (2 H, m),2.50 (210,260 3H, 8), 264 2 H.0), 268 (3 H,s),.3.22.2 H,0.392(21.0,696 (TH.d). 7.19 (11.0), 735 0H. 1), 7.85-7.55 (2H. m) and 7.62 (11H, d) (Found: C, $62 1H, 5.20: 8, 6.198, 14.5%. C3,HyaN,O8,Ni requires C57 2 HE 5.48; N, 6.35: 8, 15.0%) 24, Chemical reduction ofthe nickel) complexes ‘Typically the chemical reduction ofthe nickel) com- plexes was performed by adding 3.0 g of sodium amalgam (1S ww Na/Hg) to 10 cm? of solutions = 1% 10? mol «ém- ofthe desited nickel (IE) complex in dm using strictly “anaerobic conditions. 23. Crystallography 25.1, Xeray data collection and reduction Green needles of [Ni(edMeOsalen |.0.5(p-dioxane) were formed by slow evaporation of a p-dioxane/ dichloro: ‘methane solution, The erystal-ell dimension determination and data colletion were performed on a STOE-IPDS dif feactometer, using Mo Ka radiation (A~0.71073 A), at 203 K. A summary of erystal data, experimental details and ‘refinement results are listed in Table 1 2.6. Structure solution and refinement The structure of [Ni(cdMeOsalen)].0.5(p-dioxane) was solved with SHELXS-86 [13] program by direct methods and the atomic positional and thermal parameters (aniso- tropic non-hydeogen atoms, except C18 and C19) were refined by full-matrix least-squares on F with SHELXL-92 4]. As the solvent molecule is disordered the atoms C18 and C19 were refined isotopically. and 03 was refined ani- sotropically, Hydrogen-atom positions were calculated by idealized positions, excep for hydrogen bonded oC, which ‘was located from the difference Fourier map. Atomic scat tering factors were from Intemational Tables for X-ay CrysE Perit o/Inrsni Chimia Acta 271 988) 8592 ” [NicdheOrten | 5 psi Formlaweghe slat Cowal sysem nba ath Mansy may hase ech) 176803) Bo “0 ye) . * ose ot once (A amn3.909, Densiy (ee) (gem) ast Avon cota (em tee ‘rage er da colton") si-osa7 Range okt 15-513, IR Refecion else 599 Independent efectos 908 fg = 0.6800) Datei prumces evar Fines [> 26(07 Rinses (alta) Alte str ureter “ama ts (S46 and 0701 Largest pak aha (eA EYRE Ne Eee saber of etns panes Bet PAPERS tallography [15] and molecular graphs from SCHAKAL, (06) 3. Results and discussion ‘Methyl-2-[¥-(2'-aminethane) }-amino-I-cyclopentene- Aithiocarboxylae fs @ convenient starting, material for the symihesis of asymmetric ligands containing NSO coordina- tion spheres. Schiff base condensation of the methyl 10) 4660 282 10": 6098 (10 183 (435% 10344 (3.42% 088 21 MP. AT) 1003 (4.310) 427 a> 10") 496.2 (3043 10: 392 (298) 2040510) 442 (6.90 10) 378 (400% HP: 458 (130) $90 (46 HP) 405 (9.1710 440 (3.86% 1) 500 (230) *Molrcatnton fete how Bact, ol" et ~ntecton < Onmined om Ref 19) esis fom Rt (8 band at A = 599-615 nm, followed by several high-intensity bands at higher energy, Band masima and calculated extinction coeFciens are presented in Table 3. Bh des 750,599 S109 4888483 1021S sie aa0 S11 es 148 SODA S112 48k a71 5590 fase res 90:50 “The low-energy band stypical of d-d transitions in square planar nickel(II) complexes with mixed coordination spheres containing nitrogen and sulphur stoms (21, sug~Paria. / organic Chinon Acta 271 (1998) 82-92 ® gesting that all the mickel(T) complexes studied remain approximately square-planar, even in strong donor solvents, This is in accordance withthe 'H NMR spectra obtained in 4y-dmf, CD,CN and CDCI, which show thar the complexes are diamagnetic in these solvents; only minor differences between the spectra of the complexes and ofthe free proli- azands are observed. Consequently, coordination of solvent ‘molecules is very weak or non-existent, “The three bands observed in the region 470-400 nm are probably due toS-Niand O-NiLMCT transitions. and occur at energies similar to those found for the corresponding symmetric nickel(M) complexes [Ni¢ed.en)] [9] and [Ni(saien)} [8] (Table 3), Analysis ofthe results presented in Table 3 shows that the positions of the &- and LMCT bands ae not very sensitive ‘0 the different substituents of the ligand, and may not be Airey related to the electton donor acceptor ability ofthe substituent. This behaviour has been observed for square planar copper(II) complexes and was explained by the pos> Sible existence of both electronic and structural effects induced by the substituents, which may have opposite effects [22]. Comparison of the molecular structure of [NiCed- salen) } [19], and [Ni(cdMeOsaien)] shows that, forthe asymmetrical complexes reported here, intewdution of sub- stituents inthe phenolate ring may induce different tetahe~ ral distortions, which may be opposite to the electronic substivent effect. Consequently. and inthe absence of struc ‘ural data forall the complexes, it isnot possible to rtionaize ‘he small diferences in band postion forall the nickel) complexes sdied 33. Celie vltanmeiry “The voltammetric behaviour ofthe nickel(I1) complexes ‘and the parent ligands was studied in dmf solutions inthe potential range +14 t —2.1 V and selected results are summarize in Table 4 “rts ‘Vola prnees tine fr the ick) comgenes* Fe. 2 Cyc volammogams of th flowing saan (a) 1 0M Hessler and 01 M TBAP io ds (8) bt [Sil] and 0, "THAP mnt employing aan re of 2005p cet ‘Se ABIApCT eeene eed 331, Ligands A ypical voltammogram of the ligands studiedispresented in Fig. 2 At potentials ranging trom +0.98 19 + 1.24 V one anodic wave is observed (wave 1), coresponding oa totally lnreversible charge transfer. Coupled with this anodic wave, ‘one cathodic wave of lower intensity at potentials —1.1 to 1.2 V (save Il) is seen in the reverse scan, except for HcdCl,salen which shows two coupled eathodic waves at =0.6andat ~ 1.6V. Multple scanning nthe potential range + Lato — LBV shows thatthe voltammeiric waves are not repeatable, and that curent intensities decrease in subsequent cycles. This behaviour is also found in several mercaptans. and has been attributed tothe oxidation ofthe thiol group 0 ‘the corresponding disulphide, for which the peak at ~ 1.1 V thas been ascribed to the reduction of the disulphide tothe ‘corresponding thiolate (28). The decreas incurrentintensty ‘may be explainedby a slow decompositionreactioninvolving ‘the disulphide species, yielding a soli product that deposits a the electrode surface, a is detected by lectode Fouling a the end ofthe voltammetric experiments, ‘Cyclic voltammograms obtained in the potential range +02 w 21 V show one ill-defined cathodic wave at approximately 2.0 V, except for Hsednapen and H,cdMenapen, the voltammograms of which show two con- compen may ar BAM) Ent) SE) irictatey) vom 008 “ie isis 18 owes treaty) tom Coo Tim “iat Tigi igs fame aor thicivcores)) 0g? 080 iM Thao iSts iS bows 80 tice Sage “osti-ose 13h “uhs “hg Thame Bosse [Scioconlce)) 088 088 Tz Tigo TiS iss toe Oa {icumeseouies}] S08} ~baS Tile Tine That Tiget aes {Scant soo Loar tz cua 10 TLS opr {cnc yoo 95 Tis tem “tse ham agra iedenpey) = 0D 085 TiS Tess Ties Thee Goma tween som [Yeo Tusa Tish oma “owns pone n Vive wo Al AgCI 1 to dn? NACL lees ecto and cone othe BF ope (bg + Ey gs tales were baseline coed“0 Rereirget al trsoica Chimica Acta 27 (198) 8-92 secutive cathodic waves, In the reverse scan one anodic wave at =00 V is observed, with a current intensity of approxi ‘mately 20% ofthat ofthe cathodic peak, with the exception fof Hyed( MeO j salen, H.edMeMeOsalen and HacdClsalen, for which no anodic wave isdetected. Cyclic volammograms ‘obtained for Heedzen and other related ligands containing the methyl 2-aminocyclopentenedithincarboxylate lragment show a reduction behaviour similar to the present ligands (sce supplementary material), in eentrast to Hysalen and substiuied derivative, which’ do-not show any reduction wave before solvent discharge. Thus, the cathodic wave ‘observed may be assigned to the reduction ofthe methyl-2- aminocyelopentenedihiocarboxs/ate fragment. 3.3.2. Nickell) compleres “The oxidation behaviours similar to that observed forthe ligands, but with £,, values 0.2 1 04 V more negative than for the somespooding free ligands (Fig. 2). Similarly, after several voltammetre cycles a solid product is deposited at the surface ofthe electrode. This observation suggests that the oxidation of these nickel(IE) comp exes iva ligand-based. process that leads to decomposition of the complex. The samme type of electrochemical behaviour was observed for INiced.en)] [9], but is in contrast to the behaviour of Aickel(I}) complexes with Schiff bases derived from sali- cylaldehyde and naphthaldehyde, which show a reversible one-electron oxidation process) with the formation of nickeICHL) complexes [8.24] “The cyclic voltammograms obtained in the potential range 00 19 2.1 V ar indicative ofa reversible heterogeneous electron transfer occurring at potentials in the range ~ 144 to ~ 1.67 V (Fig. 2). The eathotie-anodie peak separation is comparable to that observed forthe Fe™ Fe couple under the same experimental conditions. Stuy of the dependence ‘of the voltammetic parameters with sn rate inthe interval 10-500 mV s™! shows: (a) a linear relationship Of pap With "3 and (b) a small dependence of Ey. with sean rate {Egep 8 proportional 0 pace) that may’e attributed solely to ohmic potential drop dc to the high resistance of the solvent used. The rao jplip ate Close 10 unity, exept For Ni(edCl:salpd) ]. whict exhibits jy ratios always Tess ‘han 08, Thslatter behaviour may beex lained by additional errors involved in the determination of «odie peak currents, due to the proximity of the eathodie wave associated with Tigand reduction, EPR spectra of th: electtochemically reduced solutions show that the redox process corresponds in all cases to a Ni"/Ni! conversion (see Szction 3.4). Cyelie volammograms of [Ni(salen'] and INited.en)] Solutions in dmf/TBAP 0.1 mol dra” * were also recorded in the interval 0.010 ~ 21 Vand for both complexes areversible redox process is observed with E,» vilues of —1.70 and “1.56 V, respectively, in agreement with previously reported values [9.25} ‘Our data suggest that there are three factors that conteibute tothe accessibility ofthe ~ I oxidation state for nickel. Fist, substitution of phenolat by softer thiolate donors results in adecrease of Ey; values of = 0.07 V. Secondly. introduction bf eleetron-acceptor substituents als results in more positive Ea values tor the Ni¥/ Ni process. This fects even more pronounced than the observed stabilization ofthe nickel(1) complexes when the oxygen donor is replaced by a sulphur In he coordination sphere of the complex. As an example, By for [Ni(edClsalen)) is 0.21 V more postive than for [Ni(edsalen) | Finally an increase of the aromatic character ‘ofthe ligand also resus ina relative stabilization ofthe +1 ‘oxidation state of nickel, but dis effect i less important as can be seen by noting that substitution of the phenolate ring bby a naphtholate ring {[Ni(edRsalea)] versus [Ni(cdR- ‘napon) | only increases the Bx value by =0.05 V. 34, EPR of electrochemically and chemically reduced solutions ofthe nickel eomplees Electrochemical reduction of nickel( I) complexesindmt was followed by coulometry, under stitly anaerobic con- ditions and using previously dried solvents, Total charge at the end of the electrolysis corresponds, in all cases, to one electron reductions ofthe nickel(IT) complexes, Duringelec~ twolyss the solutions cura from light green to dark green oF blue, and the new solutions exhibit a brood EPR signal, a room temperature, With g 212, thus eonfiming thatthe redtion occurs at the metal centre (Fig. 3). Chemical ‘eduction using Na/Hg amalgam yiclds solutions with iden- tical EPR spectra. Frozen-solution EPR spectra exhibit a shombie signal (Table 5, Fig. 3), with g,* g= 8s typical of nickel(D) complexes with ad. oFad,, ground state [26-30]. Inthe high-field region ofthe spect hyperfine coupling with wo, magnetically equivalent nitrogen nuclei (""N, 7=1) is tbserved, in accordance with the similarity between the two. nitrogen donor stom revealed inthe molecular structures oF these complenes (19.20), EPR spectra of the nickel(1) complexes show a significant dependence ofthe g values with the coordination sphere of the ligand, with a reduction of ¢ values with increasing num ber of sulphur atoms in the coordination sphere ofthe com: plexes, bu are almost independent of te substituents ofthe ligand. eae DA Fig. 3 EPR spaces of an cecal eed sation of (i Sa) find a tare epee 8) 3177Perea. Ingenio Chimica Ac 271 (198) 89-92 o Exprinetal EPR pretest ikl) compen” INitcsaten| 2a 2086 | ou pe 95 12 (lees 23 oi bowe ae fo o8 [NicaNeOsale) oer owe 2 ns [NitciMesaien) | 2au Sosa dows bia +0 3 [SiestseO ale) 2005 200 2m ns INitsiMeNeOsten) | 225 ost 200 2m 20 3 [NiesChalet || 0 ose zou im %o oo [Niteiapen 228 oss 20 2a oS oe [NiedMenie) | ahs 2079 200 Bie Ay Niven) 28 207 206 208 so [Niele 29) ost 200 Bint “ype coupling constant a 10-42! Nasr REE 251 4. Conclusions ‘The nickel(I1) complexes synthesized in this work were shown to have amixed donor N,OS coordination sphere with napproximate square-panar geometry. Cyclic vollammetic studies revealed that in the potential range studied the nickel(IL) complexes may be oxidized and reduced, but while the reduction process occurs a the metal centre and yields nickel (1) complexes, the oxidation is probably ligand based ‘Spectnascopic characterization of the complexes in solid and in solution shows thatthe structure of the complexes, remains essentially unaltered, even in strong coordinating solvents. Another aspect tobe stressed isthe relative insen- sitivity ofthe spectroscopic characteristics ofboth nickel( I) and nickel(1) complexes to substivents on the salicylate ragments in contrat to what i observed forthe reduction potentials. Since the spectroscopic propetis of the metal ‘complexes are expected to be highly dependent on the energy ‘ofthe metal oebital involved in a-interaction withthe ligands, ‘these results imply thatthe dependence of reduction poten tials on substituents is related either othe acceptor ability of the ligand and/or to a tetrahedral distortion of the hickeI(M}) complex. Compating X-ray difraction and vol- tammetric results forthe present complexes, it is apparent ‘that both Factors must be important inthe stabilization ofthe +1 oxidation state for nickel: (a) [Nifedsalen)] and UNi(cdnapen) | show similar tenahedral distortions, but the later is reduced at more positive potentials, as expeeted fom itshigher acceptor ability: (b) [Ni(cdMeOsalen) ], which hhas 8 more pronounced tetrahedral distorion than [NiCedsalen}].ismore easily reduced, altrough te electton- Alnor ability of the substituent would have predicted more negative reduction potential for the former complex. ‘Voltammeteic daa suggest thatthe replacement of oxygen by sulphur atoms stabilizes the + 1 oxidation state for nickel For the three non-substitated complexes. [Ni(salen)}. Ni(edsalen)} and [Ni(eden)] there is an increase of '=0,07 V in Ey» for the reduction process by each oxygen that is replaced by a sulphur in the coordination sphere. Although tiscurrently accepted that thiolate ligands stabilize high oxidation states for metal ions, low oxidation states are ‘expected to be unstailized by this kind of ligand [31.32] [Nevertheless, in ligands like those we report here and that ‘exhibit a strong = delocalization, iti possible that sulphur may actasa strong donor towards meta fons inhighoxidation states, and us a w-acceptor towards metal ions in low oxida tion states. 5. Supplementary material Lists of observed and calculated steucture factors, complete bond distances and angles, anisotropic thermal parameters for the non-hydrogen atoms, hydrogen atoms parameters and. cyclic voltammetry data for the ligands are available from the authors on request. 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