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CROATICA CHEMICA ACTA CCACAA 75 (1) 131¿153 (2002) ISSN-0011-1643 CCA-2788 Review Calixarene Complexes with Transition Metal, Lanthanide and Actinide Ions Wanda B Sliwa Institute of Chemistry and Environmental Protection, Pedagogical University, al. Armii Krajowej 13/15, 42-201 Czeu stochowa, Poland (E-mail: [email protected]) Received December 13, 2000; revised April 9, 2001; accepted May 2, 2001 Selected calixarene complexes with transition metal as well as lanthanide and actinide ions are described, showing their syntheses and possible applications. Key words: actinides, calixarenes, complexes, lanthanides, nickel, platinum, rhodium, tantalum, transition metals, tungsten. INTRODUCTION Due to their structure and properties, calixarenes are a topic of many works.1-8 Numerous metal ion complexes of calixarenes are known,9-14 among them those with transition metal ions.15-18 Title complexes are interesting from both theoretical and practical viewpoints, for example they are used in the extraction of lanthanides and actinides from nuclear waste.19,20 The following complexes are described in the present review: – calixarene complexes with nickel, copper, zinc and silver ions, – calixarene complexes with chromium, tantalum, tungsten and niobium ions, – calixarene complexes with lanthanide and actinide ions, – calixarene complexes with ruthenium, rhodium, palladium and platinum ions. References of works that appeared during the years 1998-2000 are cited. W. bSLIWA 132 CALIXARENE COMPLEXES WITH NICKEL, COPPER, ZINC AND SILVER IONS Nickel-thiolato-calixarene complexes have been investigated.21 The reaction of dichloroethylcalix[4]arene (1) with nickel(II)thiolate (2) in the presence of NaI affords nickel(II) and bis-nickel(II)-calixarene complexes (3 and 4), Scheme 1. S N HO O OH O 2 1 HO O OH O S S O + 2I - HO OH O 2I - S S N N S S Ni Ni Ni N S N Cl Cl NaI / MeCN Ni + N N N 4 3 Scheme 1. Nickel ion can be removed from complex 3 by treatment with KCN. The formed free ligand 5 of a crown ether structure contains two nitrogen, two oxygen and two sulfur electron-donors convenient for further complexation (Scheme 2). O HO OH O O HO OH KCN / MeCN S S S S Ni N N 2I - N N 3 5 Scheme 2. O 133 CALIXARENE COMPLEXES In the study of fluorescent chemosensors for optical detection of transition metal ions, bispyrenylcalixarene 6 has been synthesized.22 This compound exists in CDCl3 solution at room temperature as a mixture of cone and partial cone conformers 6a and 6b (Scheme 3). Me O O O Me R O R O O Me R O R O Me 6b 6a OH N * O R= Scheme 3. Fluorescence intensity in methanol-water solution is sensitive to pH and the presence of transition metal ions. Addition of Cu2+ and Ni2+ ions induces a strong, pH dependent quenching of fluorescence of 6. Calixarene 6, acting as an excimer-forming photoresponsive ligand is therefore a selective chemosensor for the detection of Cu2+ and Ni+ ions. The proton induced decomplexation makes it possible to distinguish CuII and NiII ions in solution via fluorescence emission enhancement.22 Dinuclear CuII and ZnII complexes 7 and 8 (Scheme 4) have been investigated as enzyme models of phosphodiesterase.18,23,24 Me 2+ Cu N Me N HO Cu2+ N N N N Me Me O O N OO O O Me Me Me N N N Zn 2+ Zn 2+ N N Me OH O Me N N O O O 7 OO O O 8 Scheme 4. O O Me W. bSLIWA 134 Soft metal ions, such as Ag+, have high affinity to p-coordinating groups, e.g. to allyl or phenyl. t-Butyl[4]arenes have been chosen as examples of such neutral carriers containing p-coordinating substituents for Ag+ sensors. It was observed that tetraallylether 9a has good ionophoric properties; it shows very high silver ion selectivity against sodium ion. The calixarene tetraallylester 9b, however, has only low silver ion selectivity with a considerable sodium ion interference (Scheme 5).25,26 4 OR R 9a 9b O O Scheme 5. Selenium containing calixarenes 10 and 11 have been synthesized and their complexing abilities have been investigated.27 For comparative purposes, sulphur and oxygen analogues of 10, i.e. calixarenes 12 and 13, have been prepared (Scheme 6).27 The highest Ag+ extraction selectivity was found for selenium calixarenes 10 and 11, and for sulphur compound 12, while oxygen calixarene 13 shows only very low affinity to Ag+ ion. These complexing properties of selenium calixarenes are of interest in their application for the detection of Ag+ ions O HO OH Y O O Se Y 10 12 13 HO Y Se S O Me Se Me 11 Scheme 6. OH O 135 CALIXARENE COMPLEXES and for the recovery of Ag+ from industrial waste water.27 A rather unexpected observation was that there was almost no affinity of calixarenes 10–13 towards Pb2+ ion, whose size is similar to that of Ag+.27,28 In order to obtain calixarene based ion-selective electrodes sensitive to soft heavy metal ions such as Ag+, Pb2+ and Hg2+, calixarene should be functionalized with groups containing nitrogen and sulphur atoms; in this case, the binding of soft heavy metal ions is higher than that of alkali metal ions. For this purpose, compounds 14a,b bearing benzothiazolylthioalkoxy moieties have been synthesized by treating calixarenes 15a,b with 2-mercaptobenzothiazole (Scheme 7).29 Calixarenes 14a,b adopt cone conformations; it was found that they are convenient ionophores for silver ion-selective electrodes.29 SH N S HO O HO O O OH nX NaHCO 3 n S n Y N 15a 15b X Y n Cl Br Br Br 1 2 O OH n S S S 14a 14b N n 1 2 Scheme 7. CALIXARENE COMPLEXES WITH CHROMIUM, TANTALUM, TUNGSTEN AND NIOBIUM IONS In the study of the calixarene chromium complexes, the reaction of 16 with [CrCl3(thf)3] leading to [Cr{p-t-Bucalix[4](O)2(OMe)2}(Cl)(thf)] was carried out (Scheme 8).30 [CrCl3(thf)3] MeO NaO O O OMe MeO ONa OMe Cr Cl THF 16 17 Scheme 8. W. bSLIWA 136 Complex 17 reacts with LiMes and NaCp to give mesityl and cyclopentadienyl derivatives 18 and 19, respectively (Scheme 9).30 Complex 18 crystallizes with toluene in 1:2 ratio, one toluene molecule being hosted in the calixarene cavity. O O O OMe MeO O OMe MeO Cr Cr Me Me 19 Me 18 Scheme 9. The reactivity of CrIII in 18 and 19 is very low, even under photochemical or thermal conditions. Compound 17, however, undergoes one electron reduction leading to 20 by treatment with sodium in the presence of naphthalene in THF. Complex 20 crystallizes with THF in 1:2 molar ratio, one of the two THF molecules being encapsulated in the calixarene cavity. This species is air sensitive, it readily undergoes oxidation to give 21 via a bridged peroxodichromium derivative 22, undergoing a cleavage of the O–O bond (Scheme 10).30 O 17 1. O2 in n-hexane 2. toluene reflux Na / C 8H10 O O O OMe MeO Cr THF O O OMe O Cr Cr MeO O O OMe Cr Cr O O MeO O MeO OMe MeO O O OMe 20 22 21 Scheme 10. The reaction of calixarene 23 with TaCl5 affords the bis-tantalum complex 24, and the reaction of 25 with TaCl5 results in its demethylation leading to complex 26 (Scheme 11).31 137 CALIXARENE COMPLEXES O O TaCl5 HO OH OH O O Cl Ta Ta Cl O OH O O O 23 24 TaCl5 MeO HO OH O OMe O O MeO 25 Ta Cl Cl 26 Scheme 11. The alkylation of 24 gives 27a-c, which are in equilibrium with their monomeric forms 28a-c. Similar alkylation of 26 leads to 29a-c, which in the presence of pyridine undergo demethylation to give 28a-c (Scheme 12).31 26 RMgX or RLi 24 RMgX or RLi O O O MeO Ta O O R O 29a 29b 29c O R Ta Ta R O O O O R pyridine O R 27a Me 27b CH2Ph 27c p-MeC6H4 O O Ta R R 28a Me 28b CH2Ph 28c p-MeC6H4 Scheme 12. O W. bSLIWA 138 Complex 26 may be used for the synthesis of derivatives containing unsaturated carbon groups bonded with metal, as shown in Scheme 13.31 L L Li 26 LiC CPh O LiC O CPh / Et2O O MeO O O Ta Ta C C C C O MeO C C Ph C Ph Ph Ph C C C Ph L = Et2O Scheme 13. The reaction of 26 with Mg(C4H6) leads to the tantalum-butadiene complex 30, converted by treatment with acetone into dioxo metallacycle 31 (Scheme 14).31 26 Mg(C4H6) O O MeO Me2CO O O O O MeO Ta Ta O Me Me 30 O C Me C Me 31 Scheme 14. In the study of tungsten complexes of calixarenes, the following reactions of 32 were performed (Scheme 15).32,33 It was observed that complex 33 reacts with Ph3SnCl to give 34, useful in transmetalation reactions with transition metal derivatives.34,35 The reaction of 33 with phosgene affords the ketenyl derivative 35, which by treatment with another molecule of 33 gives an equimolar mixture of 36 and 37; this reaction proceeds via intermediate 38 (Scheme 16).34 139 CALIXARENE COMPLEXES + B(C6F 5)3 O O O O W [MeB(C6H5)3] - Me O O O O ZnMe2 O O W W Me Cl Cl O O Me 32 O SnCl4 O O O W Me Cl Scheme 15. Ph3SnCl O O - O O W C Ph SnPh3 34 O O O O W C + Mg 0.5 . 6 THF Ph COCl2 O O 33 O O W Cl C C O Ph 35 - O Ph C W C O Ph 35 C 33 Cl W O O O O O O O - Cl- O O O O W C 36 Scheme 16. O 37 Ph 38 O O C Ph O W C + Mg 0.5 . 6 THF + O W. bSLIWA 140 Complex 33 may be used for the synthesis of phosphanylalkylidenes and their transformation into dimetallic complexes; its reaction with ClPPh2 gives 39, which by treatment with [(thf)Cr(CO)5] and [CuCOCl] affords dimetallic complexes 40 and 41, respectively (Scheme 17).34 [(thf)Cr(CO)5] O O O O W C P Cr(CO)5 Ph2 Ph 40 33 ClPPh2 O O O O W C Ph [CuCOCl] PPh2 39 O O O O O O O W W C Ph O C Cl P Cu Ph2 Ph P Ph2 Cl 41 Scheme 17. Oxidation of 33 by I2 leads to complex 42, in which the iodine atom may be replaced by various organometallic nucleophiles. For example, the reaction of 42 with NaNMe2 affords aminoalkylidene 43 (Scheme 18).34 NMe2- I2 33 O O O O O O W C Ph O O W C I NMe2 Ph 42 43 Scheme 18. 141 CALIXARENE COMPLEXES Treatment of complex 32 with butyl carboanion gives rise to alkylidyne 44, which was converted into alkylidene 45 by protonation (Scheme 19).36 _ Bu32 O O O H+ _ + H O O O W O O W C C Pr Pr H 45 44 Scheme 19. The following reactions (Scheme 20) of 32 have also been performed.32,35 Na O O O Na O O O O O W W Cl Cl 32 O O W O O O O O O W hn C t-Bu C H Scheme 20. Activation of small molecules like O2, N2, CO and CO2 by metallacalixarenes is possible; an example of dinitrogen activation and cleavage is shown (Scheme 21).36,37 W. bSLIWA 142 O O Na 2- O O O O L L L Na O Nb Nb 1. N2, THF 2. digly L L O O O O O O 1. Na / THF Nb 2. O N O N Na L O O O O O O Nb O Na N N O O Na O Nb Nb O O O O O O O L = THF 2[Na(digly)]+ digly = O O Na O O O Scheme 21. CALIXARENE COMPLEXES WITH LANTHANIDE AND ACTINIDE IONS Lanthanide complexes of calixarenes have been investigated.38,39 Complexation of trivalent lanthanide ions by calixarenes is promising in terms of their use for the design of luminescent devices and for the extraction of lanthanide ions from nuclear waste. It was observed that calixarenes with phosphorus-containing pendant arms40 are better extractants for lanthanides(III) and actinides(IV) than TOPO (trioctylphosphine oxide) or CMPO ((N,N-diisobutylcarbamoylmethyl)octylposphine oxide) used in the nuclear waste management. Calixarene 46 forms with Ln3+ ions (Ln = La, Eu, Tb) 1:1 hydrated and anhydrous complexes 47 and 47' as well as 2:1 complexes 48 (Scheme 22).40-42 In the hydrated 1:1 complex 47a the La3+ ion is coordinated by the four P=O groups and by water molecules, while in the anhydrous complex 47'a the La3+ ion is situated deeper in the calixarene cavity. In the study of extractants for lanthanides and actinides contained in nuclear waste, calixarene 49 (Scheme 23), functionalized at the upper rim by CMPO analogue, was investigated.43 Calixarene 49 is a more powerful extractant than CMPO and shows high selectivity for lighter lanthanides and actinides.44 For this purpose, calixarenes 50 (Scheme 23) functionalized 143 CALIXARENE COMPLEXES O O O O P P Me Me Me Me O Me P Me Me O Me O O 46 P O Me2 P Me2 P OO O O O O O O Me2P P Me2 O Me2 P PMe2 O O O O P Me2 O O PMe2 = Ln3+ anhydrous Ln 47'a La 47'b Eu 47'c Tb hydrated Ln 47a La 47b Eu 47c Tb O O O Me2 P O Me2 P O O P Me2 O O P Me2 Me2 P Me2 O P O O O O P Me2 O O P Me2 O Ln 48a La 48b Eu 48c Tb Scheme 22. W. bSLIWA 144 Ph Ph O P Ph O N O Oct P Ph O O P Ph O P Ph Ph O O NH O NH O HN Ph O P Ph NH O O O O (CH2)n NH NH CMPO O O O O O Ph P O Ph O O (CH2)n O (CH2)n (CH )n 2 NH O Ph P O Ph NH O P Ph O O P Ph Ph O Ph n 50a 2 50b 3 50c 4 49 Scheme 23. by CMPO analogue at the lower rim are also promising. It was found that calixarenes 50 show increased extraction of La3+, Eu3+, Yb3+ and Th4+. Compounds 49 and 50 are selective extractants of thorium over lanthanides, 50b being the most selective extractant for Th4+/Eu3+ and Th4+/La3+.45 Calixarenes 51a-f (Scheme 24) bearing phosphine oxide moieties have been investigated in view of their complexing properties towards trivalent lanthanides (exemplified by europium(III)) and tetravalent actinides (exemplified by thorium(IV)), separations of lanthanides and actinides being of great importance in the management of nuclear waste.46 Calixarenes 51a and 51d exist in stable cone conformations in solution, while compounds 51a,c,e,f are conformationally mobile. R 4 O PPh2 51a 51b 51c 51d 51e 51f R t-Bu t-Bu t-Bu H H H n 4 6 8 4 6 8 O Scheme 24. It was established that calixarenes 51a-f are more efficient extractants for europium and thorium than TOPO and CMPO, with the exception of europium extraction by 51c. Extraction of europium is lower than that of thorium. Dealkylated calixarenes 51d-f are more efficient than alkylated compounds 51a-c for both europium and thorium extraction.46 145 CALIXARENE COMPLEXES CALIXARENE COMPLEXES WITH RUTHENIUM, RHODIUM, PALLADIUM AND PLATINUM IONS Complexes of calix[4]arenes 52-54 (Scheme 25) containing phosphine moieties have been investigated.47,48 O Ph2P O O Ph2P O O O Me PPh2 PPh2 O Ph2P 52 O O O PPh2 PPh2 Ph2P Ph2P OH OH 54 53 Scheme 25. Reactions of 52 with [Mo(CO)3(C7H8)] and [RuCl2(dmso)4] lead to complexes 55 and 56, compound 53 treated with [Mo(CO)3(C7H8)] and with AuCl(tht) (tht = tetrahydrothiophene) affords complexes 57 and 58, and calixarene 54 reacts with [PtCl2(cod)] (cod = cycloocta-1,5-diene) to give 59 (Scheme 26). O O Ph2P O O Ph2P Ph2P PPh2 Ph2P Mo OC C O O O Ph2P O Ph2P O PPh2 Ru CO Cl Cl 56 55 O O Me O O PPh2 PPh2 Ph2P C O 57 Au CO O O O Ph2P Mo OC O O Me Ph2P PPh2 Au Au Cl Cl Cl 58 Scheme 26. PPh2 Cl Cl Pt O OH PPh2 59 OH W. bSLIWA 146 Treatment of 52 with [PtCl2(cod)] results in formation of 60, which could not be isolated due to oligomerization. To prevent oligomerization, the mild oxidation of uncoordinated phosphine groups by addition of urea · H2O2, leading to 61, may be applied. Another method involves complexation of the remaining phosphine groups with [AuCl(tht)], affording the trinuclear complex 62 (Scheme 27). H2NCONH2 . H2O2 O O Cl Cl 52 Pt PPh2 PPh2 O O PPh2 O PPh2 O 61 [PtCl2(cod)] O O PPh2 Pt Cl Cl O O PPh2 PPh2 PPh 2 60 O O AuCl(tht) Cl Cl Pt O PPh2 PPh2 O PPh2 Au Cl PPh2 Au Cl 62 Scheme 27. Using the first procedure, the reaction of 53 with [PtCl2(cod)] and the subsequent oxidation with urea · H2O2 leading to 63 were performed (Scheme 28). Me 1. [PtCl2(cod)] 2. H2NCONH2.H2O2 O O O O PPh2 O O Ph2P Me Ph2P O O PPh2 63 53 Scheme 28. Ph2P O PPh2 Pt Cl Cl 147 CALIXARENE COMPLEXES In complexes 59 and 61–63, the platinum centre is a part of a 12-membered metallamacrocycle.47 It was found that P-bridged calixarenes La,b form rhodium complexes with [Rh(CO)2(acac*)] (acac* = t-BuCOCHCO-t-Bu) which are catalysts of the following hydroformylation reaction (Scheme 29).49 O CO / H2 / Rh catalyst R R + R O Scheme 29. Calixarenes La,b were synthesized from compounds 64a,b by treatment with CF3COOH (Scheme 30).50 Calixarenes La,b are thermally stable even in refluxing toluene and are not hydrolyzed by aqueous HCl or NaOH.50 R R R R R R R OH CF3COOH HO O P O O + NHMe2 O - [CF3COO][NH2Me2] O O P R R La H Lb t-Bu R 64a H 64b t-Bu Scheme 30. Dissolved in CH2Cl2 calixarenes La,b were treated with [Rh(CO)2(acac*)] to give complexes 65a,b while the reaction of Lb with [Rh2(m-Cl2)(CO)4] afforded a 1:4 mixture of cis-66 and trans-66 (Scheme 31).51 O OC OC L O L 65a 65b Cl Rh Rh Lb OC CO Rh Cl Lb cis - 66 La Lb Scheme 31. Cl Rh + Lb Lb Rh Cl trans - 66 CO W. bSLIWA 148 Rhodium complexes of La and Lb were tested as catalysts of the hydroformylation of 1-hexene. It was found that they are very active and chemoselective catalysts, however their regioselectivity is low.49-51 Calixarenes 67–70 (Scheme 32) form with [Rh(CO)2(acac*)] very active catalysts for hydroformylation of 1-octene, their efficiency being influenced by the conformation of the ligand.49,50,52 O O P RO O R 67 68 69 70 i -Pr CH2Ph C(O)Me C(O)Ph Scheme 32. It was established that also palladium, iridium, platinum and gold complexes of La and Lb are promising with regard to their use as hydroformylation catalysts.49-51 Reaction of La with [PdCl2(NCPh)2] affords 71, while Lb gives binuclear palladium(II) complex 72 under these conditions, the latter being converted into 73–75 by ligands A (A = CO, MeCN, t-BuCN) (Scheme 33). La Cl Cl La Cl 71 Lb Lb Cl Pd Pd Pd Cl 72 Cl Cl Lb 73 74 75 Cl Pd A A CO MeCN t-BuCN Scheme 33. Calixarenes La and Lb react with [Ir2(m-Cl)2(cod)2] to give complexes 76a,b and the reaction of La with K[PtCl3(C2H4)] results in mononuclear species 77, while in the case of Lb the binuclear platinum(II) complex 78 is formed (Scheme 34). Treatment of La and Lb with [Pt(nor)3] (nor = h-norbornene) in CH2Cl2 leads to non-isolable mixtures of complexes 79a,b and 80a,b,50,53 and complexes 81a,b are obtained with [AuCl(tht)] (Scheme 35).50 149 CALIXARENE COMPLEXES Cl La Ir Cl Cl Pt L La L 76a 76b Cl Pt Cl Pt Lb Cl 77 Lb Cl 78 La Lb Scheme 34. L Pt L Pt L L L La Lb 79a 79b 80a 80b L La Lb Au Cl 81a 81b L La Lb Scheme 35. In the study of selective extraction of uranium dissolved in seawater in the form of uranyl cation UO22+, it was observed that the biscalix[4]arenebased receptor 82 binds and extracts uranyl cation into organic solvent media.54 The complexation of uranyl proceeds as follows (Scheme 36). O HO OH O UO2(OAc)2(H2O)2 O COOH HOOC - AcOH - H2O O HO HO O OH O O 82 Scheme 36. O U O O HO O OH O O OH O W. bSLIWA 150 The synthesis of 82 involves condensation of calix[4]arene 23 with methyl 2,6-bis(bromomethyl) benzoate leading to dimer 83 and trimer 84; the hydrolysis of the former affords receptor 82 (Scheme 37). COOMe + HO HO OH Br K2CO3 / MeCN Br OH 23 O HO OH O O HO OH O COOMe MeOOC R R + O O O OH OH O HO HO OH OH O O COOMe R 83 COOMe 1. t-BuOK / DMSO 2. HCl / H2O 84 82 COOH Scheme 37. CONCLUSION Investigations of calixarene complexes with transition metal as well as lanthanide and actinide ions are developing rapidly. In the above paper, an attempt has been made to present a concise survey of this theme. The described species are attracting growing attention, among others due to their usefulness in nuclear waste management, important in environmental protection. 151 CALIXARENE COMPLEXES REFERENCES 1. C. D. Gutsche, in: J. F. Stoddart (Ed.), Calixarenes Revisited, Monographs in Supramolecular Chemistry, The Royal Society of Chemistry, Cambridge, 1998. 2. 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