SYNTHESIS AND SELECTIVITY IN METAL-ION COORDINATION OF THE NEW LIGANDS 1,4,7-TRIMETHYL-1,7-BIS(4-CARBOXYBENZYL)-1,4,7-TRIAZAHEPTANE (L) AND 1,4,7,16,19,22-HEXAMETHYL-1,4,7,16,19,22-HEXAAZA[9.9]PARACYCLOPHANE (L1) - CRYSTAL-STRUCTURES OF [PDLH(2)CL]NO3-CENTER-DOT-2.6H2O AND [CU(2)L1CL(2)](BPH(4))(CLO4)CENTER-DOT-CH3CN

被引：27

作者：

BAZZICALUPI, C ^{[1
]}

BENCINI, A ^{[1
]}

BIANCHI, A ^{[1
]}

FUSI, V ^{[1
]}

GIORGI, C ^{[1
]}

PAOLETTI, P ^{[1
]}

STEFANI, A ^{[1
]}

VALTANCOLI, B ^{[1
]}

机构：

[1] UNIV FLORENCE,DEPT CHEM,I-50144 FLORENCE,ITALY

来源：

INORGANIC CHEMISTRY | 1995年 / 34卷 / 03期

关键词：

D O I：

10.1021/ic00107a006

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis of 1,4,7-trimethyl-1,7-bis(4-carboxybenzyl)-1,4,7-triazaheptane (LH(2)) and 1,4,7,16,19,22-hexamethyl-1,4,7,16, 19,22-hexaaza[9.9]paracyclophane (L1) is described. The interaction of both ligands with Cu2+, Zn2+ Cd2+, and Pd2+ ions has been studied by potentiometric titrations and microcalorimetry (LH(2)/Cu2+,Cd2+) in 0.15 mol dm(-3) NaCl solution at 298.10.1 K. The stability of LH(2) complexes with these cations is rather low. Thermodynamic data suggest the N-3 moiety is the binding site for Cu2+, and Pd2+, while in the case of Zn2+ and Cd2+ the carboxylate groups seem to be preferred. X-ray data confirm the coordination site for Pd2+. Crystals of [PdLH(2)Cl](NO3).2.6H(2)O are triclinic, space group P (1) over bar (Z = 2), with a 8.472(3) Angstrom, b = 12.178(2) Angstrom, c = 14.498(4) Angstrom, a = 78.26(2)degrees, beta = 87.20(3)degrees, gamma = 77.72(2)degrees, R = 0.0727, and WR(2) = 0.2294. The Pd2+ ion, is coordinated by the three amino groups of LH(2) and a Cl- anion in a square coordination environment; the two protons are located on the carboxylic groups. L1 forms both mono- and binuclear complexes with Cu2+ in aqueous solution but does not interact with Zn2+ and Cd2+. Pd2+ complexes are also formed. Crystals of [Cu(2)L1Cl(2)](ClO4)(BPh(4)).CH3CN are monoclinic, space group P2(1)/m (Z = 2), with a = 11.526(2) Angstrom, b = 13.552(2) Angstrom, c = 18.078(6) Angstrom, beta = 96.47(2)degrees, R = 0.0823, and WR(2) = 0.2366. The two Cu2+ ions are coordinated by three nitrogen atoms of L1 and a Cl- anion in a square coordination environment, the ligand behaving as a ditopic receptor. Selectivity in metal ion binding is discussed.

引用

页码：552 / 559

页数：8

共 62 条

[1] POLYAZACYCLOPHANES - 2,6,9,13-TETRAAZA[14]PARACYCLOPHANE AS A CATIONIC AND ANIONIC RECEPTOR
ANDRES, A
BURGUETE, MI
GARCIAESPANA, E
LUIS, SV
MIRAVET, JF
SORIANO, C
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1993, (04): : 749 - 755
[2] ANDRES A, IN PRESS J CHEM SOC
[3] [Anonymous], 1974, INT TABLES XRAY CRYS, VIV
[4] A NOVEL SYNTHETIC PATHWAY FOR PARACYCLOPHANE RECEPTORS
BAZZICALUPI, C
BENCINI, A
BIANCHI, A
FUSI, V
GIORGI, C
MICHELONI, M
PAOLETTI, P
VALTANCOLI, B
[J]. TETRAHEDRON LETTERS, 1994, 35 (45) : 8469 - 8472
[5] BAZZICALUPI C, IN PRESS J CHEM S P2
[6] SELECTIVE RECOGNITION OF CARBOXYLATE ANIONS BY POLYAMMONIUM RECEPTORS IN AQUEOUS-SOLUTION - CRITERIA FOR SELECTIVITY IN MOLECULAR RECOGNITION
BENCINI, A
BIANCHI, A
BURGUETE, MI
DAPPORTO, P
DOMENECH, A
GARCIAESPANA, E
LUIS, SV
PAOLI, P
RAMIREZ, JA
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1994, (03): : 569 - 577
[7] REMARKABLE SHAPE SELECTIVITY IN THE MOLECULAR RECOGNITION OF CARBOXYLATE ANIONS IN AQUEOUS-SOLUTION
BENCINI, A
BIANCHI, A
BURGUETE, MI
GARCIAESPANA, E
LUIS, SV
RAMIREZ, JA
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (05) : 1919 - 1920
[8] THERMODYNAMIC AND STRUCTURAL ASPECTS OF THE INTERACTION BETWEEN MACROCYCLIC POLYAMMONIUM CATIONS AND COMPLEXED ANIONS
BENCINI, A
BIANCHI, A
DAPPORTO, P
GARCIAESPANA, E
MICHELONI, M
RAMIREZ, JA
PAOLETTI, P
PAOLI, P
[J]. INORGANIC CHEMISTRY, 1992, 31 (10) : 1902 - 1908
[9] SYNTHESIS AND PROTONATION BEHAVIOR OF THE MACROCYCLIC LIGAND 1,4,7,13-TETRAMETHYL-1,4,7,10,13,16-HEXAAZACYCLOOCTADECANE AND OF ITS BICYCLIC DERIVATIVE 4,7,10,17,23-PENTAMETHYL-1,4,7,10,13,17,23-HEPTAAZABICYCLO[11.7.5]PENTACOSANE - A POTENTIOMETRIC AND H-1 AND C-13 NMR-STUDY
BENCINI, A
BIANCHI, A
GARCIAESPANA, E
FUSI, V
MICHELONI, M
PAOLETTI, P
RAMIREZ, JA
RODRIGUEZ, A
VALTANCOLI, B
[J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1992, (07): : 1059 - 1065
[10] COORDINATION TENDENCIES OF A SERIES OF TETRAAZACYCLOALKANES RELATED TO 1,4,7,10-TETRAAZADECANE (TRIEN) - SYNTHETIC, THERMODYNAMIC, AND STRUCTURAL ASPECTS
BIANCHI, A
BOLOGNI, L
DAPPORTO, P
MICHELONI, M
PAOLETTI, P
[J]. INORGANIC CHEMISTRY, 1984, 23 (09) : 1201 - 1205

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