Silver(I)-Selective Thioether Ligands. Solution NMR and X-ray Structural Studies on the Interaction of 2,5,8-Trithia[9]-m-cyclophane and Related Ligands with Silver(I)

Casabó, Jaume; Flor, Teresa; Hill, M. N. Stuart; Jenkins, Hilary A.; Lockhart, J. C.; Romero, Isobel; Teixidor, Francesç

doi:10.1021/ic00126a007

Cited by 35 publications

(6 citation statements)

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“…The angles C10-C7-S1 and C1-S1-C7 are 107.48 (12) and 103.82 (9) , respectively. These bond lengths and angles are all in the normal ranges and compare well those observed in other analogues (Allen et al, 1987;Casabo et al, 1995Casabo et al, ). et al, 1955 (2.75 g, 0.01 mol) was added to a hot solution (about 323 K) of thiophenol sodium salt (2.64 g, 0.02 mol) in ethanol (30 ml), and the mixture was further stirred at 323 K for 6 h. After cooling, water (30 ml) was added and the resulting mixture left to stand for 5 h. The yellow precipitate was filtered off, washed with ethanol and water, and recrystallized from a mixture of chloroform and methanol, giving single crystals suitable for X-ray diffraction (yield 3.17 g, 75%, m.p.…”

Section: Commentsupporting

confidence: 86%

9,10-Bis[(phenylsulfanyl)methyl]anthracene

Liu

Che

et al. 2005

Acta Cryst E

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Section: Commentsupporting

confidence: 86%

9,10-Bis[(phenylsulfanyl)methyl]anthracene

Liu

Che

et al. 2005

Acta Cryst E

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“…They include the trithiabenzenophane ligand, 2,5,8-trithia(9)m-benzenophane (CSD refcode VEYNES; Groot & Loeb, 1990), and a palladium and a silver complex of the same ligand, viz. dichloro[2,5,8-trithia(9)-m-benzenophane]palladium(II) (KOMNOP; Groot et al, 1991), a mononuclear complex, and poly[[2,5,8-trithia(9)-m-cyclophane-S,S 0 ,S 00 ]silver(I) trifluoromethylsulfonate acetonitrile solvate] (ZIDPEH; Casabo et al, 1995), a two-dimensional coordination polymer. In KOMNOP, the ligand coordinates in a bidentate manner.…”

Section: Figurementioning

confidence: 99%

Crystal structures of [(μ₂-L1)dibromidodicopper(II)] dibromide and poly[[(μ₂-L1)diiodidodicopper(I)]-di-μ-iodido-dicopper(I)], where L1 is 2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane

Assoumatine

Stœckli-Evans

2020

Acta Cryst E

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The reaction of the hexathiapyrazinophane ligand, 2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane (L1), with copper(II) dibromide led to the formation of a binuclear complex, [μ2-2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane]bis[bromidocopper(II)] dibromide, [Cu2Br2(C16H24N2S6)]Br2, (I). The complex possesses inversion symmetry with the pyrazine ring being situated about a center of symmetry. The ligand coordinates to the copper(II) atom in a bis-tetradentate manner and the copper atom has a fivefold NS3Br coordination environment with a distorted shape. The reaction of ligand L1 with copper(I) iodide also gave a binuclear complex, which is bridged by a Cu2I2 unit to form a two-dimensional coordination polymer, poly[[μ2-2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane]tetra-μ-iodido-tetracopper(I)], [Cu4I4(C16H24N2S6)] n , (II). The binuclear unit possesses inversion symmetry with the pyrazine ring being located about a center of symmetry. The Cu2I2 unit is also located about an inversion center. The two independent copper(I) atoms are both fourfold coordinate. That coordinating to the ligand L1 in a bis-tridentate manner has an NS2I coordination environment and an irregular shape, while the second copper(I) atom, where L1 coordinates in a bis-monodentate manner, has an SI3 coordination environment with an almost perfect tetrahedral geometry. In the crystal of I, the cations and Br− anions are linked by a number of C—H...S and C—H...Br hydrogen bonds, forming a supramolecular network. In the crystal of II, the two-dimensional coordination polymers lie parallel to the ab plane and there are no significant inter-layer contacts present.

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“…For designing such ionophores, the optimum requirement of 2-4 soft (S or N) ligating sites 2-7 preorganized in a three-dimensional system has been emphasized. In the reported Ag ϩ selective ionophores, the presence of ether units 8-12 responsible for binding towards hard alkali, alkaline earth and borderline Pb 2ϩ cations and the possibility of the formation of sandwich or polymeric complexes [13][14][15] creating significant binding towards most soft metal ions, cause lowering of Ag ϩ selectivities. We argued that in such hosts, the absence of hard (ether) ligating sites and the presence of stereochemical or structural features which could inhibit their sandwich or polymeric complexation requiring >1 : 1 stoichiometric host-guest interaction could further enhance the Ag ϩ selectivity even against the similar sized Pb 2ϩ cation.…”

Section: Introductionmentioning

confidence: 99%

Synthetic ionophores. Part 18: Ag+ selective trithiabenzena- and dithiabenzenapyridinacyclophanes 1

Kumar¹,

Hundal²,

Hundal³

et al. 1998

J. Chem. Soc., Perkin Trans. 2

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The phase transfer catalysed nucleophilic displacement of 1,3-bis(bromomethyl)benzene, 2-methoxy-5methyl-1,3-bis(bromomethyl)benzene (2) and 1,4-bis(bromomethyl)benzene with 2-mercaptoethanol gives the respective diols 3, 4 and 12 (80-85%), which undergo intermolecular cyclodehydrochlorination with thiodiglycolyl dichloride and pyridine-2,6-dicarbonyl dichlorideؒHCl to provide m-phenylene (7-10) and p-phenylene (13-14) based crownophanes. The single crystal X-ray structures of crownophanes 8 and 13 and their NMR studies show that the m-phenylene and p-phenylene rings remain in plane and perpendicular to the macrocyclic ring both in solution and solid phases. These crownophanes offer three soft coordinating sites (3 × S or 2 × S and 1 N) conducive to complexation with Ag ϩ and the steric restrictions imposed by m-and p-phenylene rings restrict 2 : 1 (L : M) sandwich complexation required for complexation with the borderline soft Pb 2؉ cation. The crownophanes 7 and 9 extract Ag ؉ 172 and 602 times, respectively, more than Pb 2؉ . Conformational analysisThe X-ray crystal structure of crownophane 8 (Fig. 1, Table 1) shows that the m-phenylene ring remains in the mean plane of the macrocyclic ring. The substituent O᎐Me seems to play a dominant role in determining the conformation of the macroring. The bond O5᎐C18 is almost perpendicular to the phenylene ring (C11᎐C16᎐O5᎐C18 being 96.7Њ). The torsion angle S2᎐C10᎐C11᎐C16 is 86.2(3)Њ and consequently both S2᎐C10 and C18᎐O5 bonds point towards the same side with respect to the phenylene ring (Fig. 1). To avoid steric crowding the S1᎐C1 bond points in a direction opposite to the C18᎐O5 bond, the torsion angle C16᎐C15᎐C1᎐S1 being 97.8(3)Њ. The torsion angle studies indicate that out of the four possible 1,4-thiaoxa units (O᎐CH 2 ᎐CH 2 ᎐S), three are antiperiplanar [torsion angles 173.8(2)-177.1(2)Њ], whereas the fourth one (O4᎐C8᎐C9᎐S3) is synclinal [59.7(3)Њ] about the C᎐C bond. The torsion angles about the C᎐O bond are antiperiplanar and about the C᎐S bond they are synclinal with the exception of C9᎐S2᎐C10᎐C11 which is antiperiplanar. In the segments O1᎐C4᎐O2 and O3᎐C7᎐O4, the carbonyl oxygens O2 and O4 point towards opposite sides of the macro-ring mean plane. The major difference in the conformation angles in the two halves of the macroring is that torsion angle C2᎐S1᎐C1᎐C15 is synclinal whereas

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Silver(I)-Selective Thioether Ligands. Solution NMR and X-ray Structural Studies on the Interaction of 2,5,8-Trithia[9]-m-cyclophane and Related Ligands with Silver(I)

Cited by 35 publications

References 0 publications

9,10-Bis[(phenylsulfanyl)methyl]anthracene

9,10-Bis[(phenylsulfanyl)methyl]anthracene

Crystal structures of [(μ₂-L1)dibromidodicopper(II)] dibromide and poly[[(μ₂-L1)diiodidodicopper(I)]-di-μ-iodido-dicopper(I)], where L1 is 2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane

Synthetic ionophores. Part 18: Ag+ selective trithiabenzena- and dithiabenzenapyridinacyclophanes 1

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Silver(I)-Selective Thioether Ligands. Solution NMR and X-ray Structural Studies on the Interaction of 2,5,8-Trithia[9]-m-cyclophane and Related Ligands with Silver(I)

Cited by 35 publications

References 0 publications

9,10-Bis[(phenylsulfanyl)methyl]anthracene

9,10-Bis[(phenylsulfanyl)methyl]anthracene

Crystal structures of [(μ2-L1)dibromidodicopper(II)] dibromide and poly[[(μ2-L1)diiodidodicopper(I)]-di-μ-iodido-dicopper(I)], where L1 is 2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane

Synthetic ionophores. Part 18: Ag+ selective trithiabenzena- and dithiabenzenapyridinacyclophanes 1

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Crystal structures of [(μ₂-L1)dibromidodicopper(II)] dibromide and poly[[(μ₂-L1)diiodidodicopper(I)]-di-μ-iodido-dicopper(I)], where L1 is 2,5,8,11,14,17-hexathia-[9.9](2,6,3,5)-pyrazinophane