HEXANUCLEAR AND DODECANUCLEAR MACROCYCLIC COPPER(II) AND NICKEL(II) COMPLEXES WITH ALMOST PLANAR BENZENE-LIKE METAL ARRAYS

被引:73
作者
TANDON, SS
THOMPSON, LK
BRIDSON, JN
BENELLI, C
机构
[1] MEM UNIV NEWFOUNDLAND,DEPT CHEM,ST JOHNS,NF A1B 3X7,CANADA
[2] UNIV FLORENCE,DEPT CHEM,INORGAN SOLID STATE CHEM LAB,I-50144 FLORENCE,ITALY
关键词
D O I
10.1021/ic00126a022
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Template condensation of 2,6-diformyl-4-(R)phenol (R = methyl, tert-butyl) with 1,3-diamino-2-hydroxypropane in the presence of copper(lI) and nickel(II) salts and base results in the formation of novel hexacopper(II) and hexanickel(II) complexes of the 30-membered, 3:3 macrocyclic ligands (H(6)MME, H(6)MTB). The macrocyclic rings contain pseudohexagonal ''benzene-like'' arrangements of metal centers, which are linked by alternating double (mu(2)-phenoxide, mu(2)-hydroxide) and single (mu(2)-alkoxide) bridges within each ring: [Cu-6(L)(mu(2)-OH)(3)](2)X(6) . yH(2)O (L = MME: X = NO3, y = 10 (1); X = ClO4, y = 6 (2); X = BF4, y = 8 (3). L = MTB: X = ClO4, y = 8 (4); X = BF4, y = 14 (5)), [Ni-6(MME)(mu(2)-OH)(3)(H2O)(6)](2)X(6) . yH(2)O (X = ClO4, y = 4 (7); X = NO3, y = 16 (8)). Two complexes (1 and 4) are dimers, with the hexagonal fragments linked by axial interactions, forming dodecanuclear species. 1 crystallized in the triclinic system, space group P ($) over bar 1, with a = 14.482(7) Angstrom, b = 14.72(1) Angstrom, c = 12.193(4) Angstrom, alpha = 95.64(5)degrees, beta = 92.32(4)degrees, gamma = 114.85(4)degrees, and Z = 2 (R = 0.103, R(w) = 0.077). Addition of NCS to the mother liquor from the preparation of 4 led to the formation of a 2:2 macrocyclic complex [Cu(H(2)MTB)(NCS)(2)](n) (6). 6 crystallized in the monoclinic system, space group P2(1)/c, with a = 12.207(2) Angstrom, b = 14.254(3) Angstrom, c = 9.550(3) Angstrom, beta = 95.42(2)degrees, and Z = 2 (R = 0.041, R(w) = 0.035). The magnetic susceptibilities of 1, 2, 4, 6, 7, and 8 were measured in the temperature range 4-305 K. The data for 1, 2, and 4 were analyzed and reproduced by using appropriate six-spin and twelve-spin models. For the copper derivatives, the presence of intra-ring and inter-ring antiferromagnetic interactions was determined with -2J(1) = -2J(2) = 318.4 cm(-1) (1), -2J(1) = -2J(2) = 485.2 cm(-1) (2), and -2J(1) = -2J(2) = 598.8 cm(-1) (4) (six-spin model) and with -2J(1) = 303.8 cm(-1), -2J(2) = 262.8 cm(-1), -2J(3) = 20.0 cm(-1) (1), -2J(1) = 484.5 cm(-1), -2J(2) = 479.0 cm(-1), -2J(3) = 16.4 cm(-1) (2), and -2J(1) = 494.2 cm(-1), -2J(2) = 412.8 cm(-1), -2J(3) = 16.4 cm(-1) (4) (twelve-spin model), while for the nickel complexes the presence of alternating ferro- and antiferromagnetic coupling was established using a sixspin model.
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页码:5507 / 5515
页数:9
相关论文
共 33 条
[21]   X-RAY CRYSTAL-STRUCTURE AND SOME PROPERTIES OF A TETRANUCLEAR, MIXED-VALENCE MANGANESE COMPLEX OF A MACROCYCLIC LIGAND [J].
MCKEE, V ;
TANDON, SS .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (19) :1334-1336
[22]   EXCHANGE INTERACTION IN TETRAMERIC OXYGEN-BRIDGED COPPER(II) CLUSTERS OF THE CUBANE TYPE [J].
MERZ, L ;
HAASE, W .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1980, (06) :875-879
[23]   LINEAR-DEPENDENCE OF SPIN-EXCHANGE COUPLING-CONSTANT ON BRIDGE ANGLE IN PHENOXY-BRIDGED DINICKEL(II) COMPLEXES [J].
NANDA, KK ;
THOMPSON, LK ;
BRIDSON, JN ;
NAG, K .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1994, (11) :1337-1338
[24]   SYNTHESIS OF A NOVEL OCTAAMINO TETRAPHENOL MACROCYCLIC LIGAND AND STRUCTURE OF A TETRANUCLEAR NICKEL(II) COMPLEX [J].
NANDA, KK ;
VENKATSUBRAMANIAN, K ;
MAJUMDAR, D ;
NAG, K .
INORGANIC CHEMISTRY, 1994, 33 (08) :1581-1582
[25]  
PARDI L, 1993, GAZZ CHIM ITAL, V123, P231
[26]   TEMPLATE SYNTHESIS OF A MACROCYCLIC TETRACOPPER(II) COMPLEX WITH 2 BRIDGING HYDROXIDE IONS IN FACE-TO-FACE MANNER [J].
SAKIYAMA, H ;
MOTODA, K ;
OKAWA, H ;
KIDA, S .
CHEMISTRY LETTERS, 1991, (07) :1133-1136
[27]   LEAD(II) AND BARIUM(II) COMPLEXES OF A POTENTIALLY OCTADENTATE MACROCYCLIC LIGAND (H4L), CAPABLE OF PROVIDING ENDOGENOUS ALKOXY AND PHENOXY BRIDGES - THE X-RAY CRYSTAL-STRUCTURES OF [PB(H4L)][CLO4]2, [PB2(H2L)][CLO4]2, AND [(H6L)(H2O)2][CLO4]2 [J].
TANDON, SS ;
MCKEE, V .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (01) :19-24
[28]   DINUCLEAR COPPER(II) AND POLYMERIC TETRANUCLEAR COPPER(II) AND COPPER(II)-COPPER(I) COMPLEXES OF MACROCYCLIC LIGANDS CAPABLE OF FORMING ENDOGENOUS ALKOXIDE AND PHENOXIDE BRIDGES - STRUCTURAL, MAGNETIC, AND ELECTROCHEMICAL STUDIES [J].
TANDON, SS ;
THOMPSON, LK ;
BRIDSON, JN ;
MCKEE, V ;
DOWNARD, AJ .
INORGANIC CHEMISTRY, 1992, 31 (22) :4635-4642
[29]   A NOVEL ANTIFERROMAGNETICALLY COUPLED, DIMERIC, DODECANUCLEAR COPPER(II) COMPLEX INVOLVING 2 MACROCYCLIC LIGANDS EACH WITH A BENZENE-LIKE ARRANGEMENT OF 6 COPPER CENTERS [J].
TANDON, SS ;
THOMPSON, LK ;
BRIDSON, JN .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1992, (12) :911-913
[30]  
THOMPSON LK, UNPUB