Abstract
Single crystal X-ray studies are recorded for five copper(II) complexes of macrobicyclic ligands. In both [Cu(sar)][ZnCl4] (295, 170 K) determinations (‘sar’ = 3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) and [Cu(NH3)2sar]Cl4·6H2O (295 K), the ligand encapsulates the copper atom by coordinating through all six nitrogen atoms, though distortions of the primary coordination sphere from an octahedral array are both marked and quite different in the two cases. [Cu(sar)]2+ undergoes a relatively facile detachment of one ligand strand in acid solution, giving a species with a different bound-N configuration to that of the reactant and which may be crystallised in various forms. In the solid of composition Cu(ClO4)2·2HClO4·½HCl·H2O·sar (295 K) the complex present is binuclear ‘[(sarH)CuClCu(sarH2)](ClO4)6·2H2O’, with the linear CuClCu array comprising the apical bonds of a pair of square-pyramidal ClCuN4 components. In mononuclear [Cu(sarH2)(ONO2)](NO3)3·3H2O (295 K) two of the ligand strings coordinate in a quasi-square-planar array, with an approach of an anionic oxygen atom to one of the remaining opposed axial coordination sites. In the crystalline complex formed between copper(II) triflate (Cu(tfs)2; ‘tfs’ = F3CSO\( _{3}^{ - } \)) and the expanded macrobicycle Me5tricosaneN6 (Me5tricosaneN6 ≡ fac-1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7]tricosane), the ligand, despite the lack of any protonation, is found (295, 150 K) to be bound in a quinquedentate form, with one triflate-O occupying the sixth coordination site about the metal, in the mononuclear complex [Cu(Me5tricosaneN6)(O-tfs)](tfs). This contrasts with the perchlorate counterpart wherein all nitrogen atoms are coordinated within an encapsulating cage.
Graphical Abstract
Structural studies of Cu(II) complexes of macrobicyclic hexamines characterise the ready displacement of some of the N-donor atoms from the coordination sphere of the metal.
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Clark, I.J., Crispini, A., Donnelly, P.S., Engelhardt, L.M., Harrowfield, J.M., Jeong, S.-H., Kim, Y., Koutsantonis, G.A., Lee, Y.H., Lengkeek, N.A., Mocerino, M., Nealon, G.L., Ogden, M.I., Park, Y.C., Pettinari, C., Polanzan, L., Rukmini, E., Sargeson, A.M., Skelton, B.W., Sobolev, A.N., Thuéry, P., White, A.H.: Variations on a cage theme: some complexes of bicyclic polyamines as supramolecular synthons. Aust. J. Chem. 62, 1246–1260 (2009)
Sargeson, A.M.: Caged metal ions. Chem. Brit. 15, 23–27 (1979)
Sargeson, A.M.: Developments in the synthesis and reactivity of encapsulated metal ions. Pure Appl. Chem. 15, 1511–1522 (1986)
Martin, L.L., Martin, R.L., Murray, K.S., Sargeson, A.M.: Magnetism and electronic structure of a series of encapsulated first-row transition metals. Inorg. Chem. 29, 1387–1394 (1990)
Creaser, I.I., Harrowfield, J.M., Lawrance, G.A., Mulac, W., Sangster, D., Sargeson, A.M., Schmidt, K., Sullivan, J.C.: Rapid reduction of [CuII(sarcophagine)]2+ and elimination of CuI from the cage: a pulse radiolysis study. J. Coord. Chem. 23, 389–395 (1991)
Szczepaniak, L.S., Sargeson, A.M., Creaser, I.I., Geue, R.J., Tweedle, M., Bryant, R.G.: Nuclear spin-lattice relaxation of water protons caused by metal cage compounds. Bioconjugate Chem. 3, 27–31 (1992)
Bernhardt, P.V., Harrowfield, J.M., Hockless, D.C.R., Sargeson, A.M.: N-Methylated macrobicyclic hexaamines of copper(II) and nickel(II): large steric effects. Inorg. Chem. 33, 5659–5670 (1994). (penta- and hepta-methyl complexes of copper(II) respectively)
Bernhardt, P.V., Bramley, R., Engelhardt, L.M., Harrowfield, J.M., Hockless, D.C.R., Korybut-Daszkiewicz, B.R., Krausz, E.R., Morgan, T., Sargeson, A.M., Skelton, B.W., White, A.H.: Copper(II) complexes of substituted macrobicyclic hexaamines: combined trigonal and tetragonal distortions. Inorg. Chem. 34, 3589–3599 (1995)
Kundu, T.K., Manoharan, P.T.: Dynamic and static Jahn–Teller distortions in a CuN6 cage complex. Chem. Phys. Lett. 241, 627–634 (1995)
Geue, R.J., Hohn, A., Ralph, S.F., Sargeson, A.M., Willis, A.C.: A new template encapsulation strategy for larger cavity metal ion cages. J. Chem. Soc. Chem. Commun. 1513–1515 (1994)
Brown, K.N., Geue, R.J., Hambley, T.W., Hockless, D.C.R., Rae, A.D., Sargeson, A.M.: Specificity in template syntheses of hexaaza-macrobicyclic cages: [Pt(Me5-tricosanetrieneN6)4+ and [Pt(Me5-tricosaneN6)]4+. Org. Biomol. Chem. 1, 1598–1608 (2003)
Brown, K.N., Geue, R.J., Moran, G., Ralph, S.F., Riesen, H., Sargeson, A.M.: A long-lived 2E state for a Cr(III)N6 amine chromophore at 298 K: [Cr(fac-Me5-D 3htricosaneN6)]Cl3. Chem. Commun. 2291–2292 (1998)
Haller, K.J., Rae, A.D., Bygott, A.M.T., Hockless, D.C.R., Ralph, S.F., Geue, R.J., Sargeson, A.M.: Four-component intergrowth structures of the metal-ion cage complexes fac-(1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7] tricosane)M(II) diperchlorate hydrate [M(C22H48N6)](ClO4)2·xH2O, M = Ni, Zn. Acta Crystallogr. Sect. B 55, 380–388 (1999)
Hathaway, B.J.: A new look at the stereochemistry and electronic properties of the copper(II) ion. Struct. Bonding 57, 55–118 (1984)
Hitchman, M.A.: The influence of vibronic coupling on the spectroscopic properties and stereochemistry of simple 4- and 6-coordinate copper(II) complexes. Comments Inorg. Chem. 15, 197–254 (1994)
Halcrow, M.A.: Interpreting and controlling the structures of six-coordinate copper(II)_ center—when is a compression really a compression? Dalton Trans. 4375–4384 (2003)
Murphy, B., Hathaway, B.: The stereochemistry of the copper(II) ion in the solid-state-some recent perspectives linking the Jahn–Teller effect, vibronic coupling, structure correlation analysis, structural pathways and comparative X-ray crystallography. Coord. Chem. Rev. 243, 237–262 (2003)
Sargeson, A.M.: The potential for the cage complexes in biology. Coord. Chem. Rev. 151, 89–114 (1996)
Grøndahl, L., Hammershoi, A., Sargeson, A.M., Thöm, V.J.: Stability and kinetics of acid and anion-assisted dissociation reactions of hexamine macrobicyclic mercury(II) complexes. Inorg. Chem. 36, 5396–5403 (1997)
Sharrad, C.A., Grøndahl, L., Gahan, L.R.: Determination of the stability constants of mercury(II) complexes of mixed donor macrobicyclic encapsulating ligands. Dalton Trans. 2937–2942 (2001)
Bottomley, G.A., Clark, I.J., Creaser, I.I., Engelhardt, L.M., Geue, R.J., Hagen, K.S., Harrowfield, J.M., Lawrance, G.A., Lay, P.A., Sargeson, A.M., See, A.J., Skelton, B.W., White, A.H.: The synthesis and structure of encapsulating ligands. Aust. J. Chem. 47, 143–179 (1994)
Dittrich, B., Harrowfield, J.M., Koutsantonis, G.A., Nealon, G.L., Skelton, B.W.: Long tailed cage amines: synthesis, metal complexation and structure. Dalton Trans. 3433–3448 (2010)
Donlevy, T.M., Gahan, L.R., Hambley, T.W., Stranger, R.: Synthesis and spectroscopic properties of the encapsulated cobalt(III) complexes derived from the unsymmetrically substituted ligand 5-methyl-5-(4-amino-2-azabutyl)-3,7-dithianone-1,9-diamine (N4S2). Inorg. Chem. 31, 4376–4382 (1992)
Harrowfield, J.M., Sargeson, A.M., Skelton, B.W., White, A.H.: Structural characterization of a cage ligand fragmentation reaction. Aust. J. Chem. 47, 181–185 (1994)
Geue, R.J., Osvath, P., Sargeson, A.M., Acharya, K.R., Noor, S.B., Row, T.N.G., Venkatesan, K.: The reaction of a nitro-capped cobalt(III) cage complex with base: the crystal structure of a contracted cage complex, and the mechanism of its formation. Aust. J. Chem. 47, 511–527 (1994)
Osvath, P., Sargeson, A.M.: Ring opening and re-arrangement of a nitro-capped cobalt(III) cage complex with an N3S3 donor set. Aust. J. Chem. 47, 807–816 (1997)
Clark, I.J.: PhD thesis, University of Western Australia (1991)
Grøndahl, L.: PhD thesis, University of Copenhagen (1994)
Donnelly, P.S., Harrowfield, J.M., Skelton, B.W., White, A.H.: Carboxymethylation of cage amines: control of alkylation by metal ion coordination. Inorg. Chem. 39, 5817–5830 (2000)
Meyer, M., Dahaoui-Gindrey, V., Lecomte, C., Guilard, R.: Conformation and coordination schemes of carboxylate and carbamoyl derivatives of the tetraazamacrocycles cyclen and cyclam and the relation to their protonation states. Coord. Chem. Rev. 178–180, 1313–1405 (1998)
Sheldrick, G.M.: A short history of SHELX. Acta Crystallogr. Sect. A 64, 112–122 (2008)
Harrowfield, J.M., Koutsantonis, G.A., Nealon, G.L., Skelton, B.W., White, A.H.: Amphiphile structures in the solid state: complex cations with lipophilic substituents. Eur. J. Inorg. Chem. 2384–2392 (2005)
Ma, M.T., Karas, J.A., White, J.M., Scanlon, D., Donnelly, P.S.: A new bifunctional chelator for copper radiopharmaceuticals: a cage amine ligand with a carboxylate functional group for conjugation to peptides. Chem. Commun. 3237–3239 (2009)
Donnelly, P.S., Harrowfield, J.M., Skelton, B.W., White, A.H.: Carboxymethylated cage amines: coordination and lactamization. Inorg. Chem. 40, 5645–5652 (2001)
Di Bartolo, N., Sargeson, A.M., Donlevy, T.M., Smith, S.V.: Synthesis of a new cage ligand SarAr and its complexation with selected metal ions for potential use in radioimaging. J. Chem. Soc. Dalton Trans. 2303–2309 (2001)
Voss, S.D., Smith, S.V., DiBartolo, N., McIntosh, L.J., Cyr, E.M., Bonab, A.A., Dearling, J.L.J., Carter, E.A., Fischman, A.J., Treves, S.T., Gillies, S.D., Sargeson, A.M., Huston, J.S., Packard, A.B.: Positron emission tomography (PET) imaging of neuroblastoma and melanoma with 64Cu-SarAr immunoconjugates. PNAS 104, 17489–17493 (2007)
Bernhardt, P.V., Bramley, R., Geue, R.J., Ralph, S.F., Sargeson, A.M.: An expanded cavity hexaamine cage for copper(II). Dalton Trans. 1244–1249 (2007)
Lee, Y.H., Harrowfield, J.M., Kim, Y., Lim, W.T., Park, Y.C., Thuéry, P.: Functionalised azetidines as ligands: Pyridyl-complemented coordination. Dalton Trans. 434–442 (2009)
Lee, Y.H., Harrowfield, J.M., Kim, J.S., Kim, Y., Lee, M.H., Lim, W.T., Park, Y.C., Thuéry, P.: Functionalised azetidines as ligands: Species derived by selective alkylation at substituent nitrogen. Dalton Trans. 443–454 (2009)
Zhang, Q.-Z., Lu, C.-Z.: Hydrothermal synthesis of structures of two new molybdenum phosphate compounds based on Keggin cluster units. Z. Anorg. Allg. Chem. 632, 330–334 (2006)
Wang, J., Ma, P., Niu, J.: The first polyoxometalate based on Keggin dodecatungstoselenate framework supported copper(I) coordination group: [Cu2(2,2′-bpy)4Cl][Cu(2,2′-bpy)2SeW12O40]·2H2O. Inorg. Chem. Comm. 9, 1049–1052 (2006)
Seeber, G., Kariuki, B.M., Cronin, L., Kögerler, P.: Synthesis, structure and magnetism of a linear Cu–Cl–Cu entity found in [{Cu(tachH)(tach)}2(μ-Cl)]5+. Polyhedron 24, 1651–1655 (2005)
Zhang, C.-D., Liu, S.-X., Sun, C.-Y., Mia, F.-J., Su, Z.-M.: Assembly of organic-inorganic hybrid materials based on Dawson-type polyoxometalate and multinuclear copper-phen complexes with unique magnetic properties. Cryst. Growth Des. 9, 3655–3660 (2009)
Bulach, V., Mandon, D., Fischer, J., Weiss, R., Bill, E., Butzlaff, C., Trautwein, A.X.: Structure and magnetic properties of a trinuclear copper(II)-cyclam derivative [Cu3(C10H24N4)3Cl2]Cl4·[(CH2Cl2)2·(H2O)4]. New J. Chem. 18, 709–713 (1994)
Pickardt, J., Hoffmeister, I.: Crystal structures of two copper(II) complexes: [{CuCl(C10N4H24)}2](CdCl4) and [Cu(C10N4H24)][CdCl3(H2O)2]Cl. Z. Naturforsch. B: Chem. Sci. 50, 828–832 (1995)
Pryma, O.V., Petrusenko, S.R., Kakozay, V.N., Skelton, B.W., Shishkin, O.V., Teplytska, T.S.: A facile direct synthesis of bimetallic Cu(II)Zn(II) complexes with ethylenediamine revealing different types of chain crystal structures. Eur. J. Inorg. Chem. 1426–1432 (2003) (the nitrogen ligands are 1,2-diaminoethane, and the anion [ZnCl4]2−)
Beznischenko, A.O., Makhankova, V.G., Kokozay, V.N., Dyakonenko, V.V., Zubatyuk, R.I., Shishkin, O.V., Jezierska, J.: MnO\( _{4}^{ - } \) as a source of manganese in the direct synthesis of heterobimetallic Cu/Mn complexes. Inorg. Chim. Acta 362, 1307–1314 (2009) (the nitrogen ligands are 1,2-diaminoethane and the anion [MnCl4]2−)
Bosnich, B., Poon, C.K., Tobe, M.L.: Complexes of cobalt(III) with a cyclic tetradentate secondary amine. Inorg. Chem. 4, 1102–1108 (1965)
Jackson, W.G., Sargeson, A.M.: Rearrangements in coordination complexes. Essay 11. In: De Mayo, P. (ed.) Rearrangements in ground and excited states, vol. 2, pp. 273–378. Wiley, New York (1980)
Elias, H.: Kinetics and mechanisms of metal complex formation with N4-donor macrocycles of the cyclam type. Coord. Chem. Rev. 187, 37–73 (1999)
Bell, C.A., Bernhardt, P.V., Gahan, L.R., Martinez, M., Monteiro, M.J., Rodriguez, C., Sharrad, C.A.: Copper(II) complexes of a hexadentate mixed-donor N3S3 macrobicyclic cage: Facile rearrangements and interconversions. Chem. Eur. J. 16, 3166–3175 (2010)
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Dedicated to Professor Leonard Lindoy, a multidentate chemist, like his ligands, on the occasion of his 75th birthday.
Alan M. Sargeson—Deceased.
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Engelhardt, L.M., Grøndahl, L., Harrowfield, J.M. et al. Copper(II) environments in some macrobicycle complexes at room and low temperatures: some novel binuclear chloro-bridged systems. J Incl Phenom Macrocycl Chem 71, 353–362 (2011). https://doi.org/10.1007/s10847-011-9952-3
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DOI: https://doi.org/10.1007/s10847-011-9952-3