A proposal for positive cooperativity in anion-cation binding in yttrium and lutetium complexes based on o-amino-substituted phenolate ligands. On the way to coordination polymers by self-assembly. Molecular structures of [ClLu(OAr)(3)Na] (X-ray) and [ClY(OAr')(3)Y(OAr')(3)Na] (X-ray and Y-89-NMR)

被引:22
作者
Hogerheide, MP
Ringelberg, SN
Grove, DM
Jastrzebski, JTBH
Boersma, J
Smeets, WJJ
Spek, AL
vanKoten, G
机构
[1] UNIV UTRECHT,DEBYE INST,DEPT MET MEDIATED SYNTH,3584 CH UTRECHT,NETHERLANDS
[2] UNIV UTRECHT,BIJVOET CTR BIOMOL RES,LAB CRYSTAL & STRUCT CHEM,3584 CH UTRECHT,NETHERLANDS
关键词
D O I
10.1021/ic950639h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Unique hetero(poly)metallic complexes [ClM(OAr)(3)Na] (M = Lu (3a), Y (3b)) and [ClY(OAr')(3)Y(OAr')(3)Na] (4) containing the bis (OAr = OC6H2(CH(2)NMe(2))(2)-2,6-Me-4) and mono (OAr' = OC6H4(CH(2)NMe(2))-2) o-amino-substituted phenolate ligands have been synthesized and characterized by NMR (H-1, C-13, and Y-89) and X-ray structure determinations (3a and 4). Crystals of 3a are triclinic, space group P (1) over bar, with unit cell dimensions a = 10.706(1) Angstrom, b = 14.099(2) Angstrom, c 18.882(3) Angstrom, alpha = 93.48(1), beta = 99.49(1)degrees, gamma = 108.72(11)degrees, and Z = 2. The chlorine, lutetium, and sodium atoms in 3a lie on a pseudo-3-fold axis (angle Cl-Lu ... Na = 177.82(5)degrees) around which the three phenolate ligands are arranged in such a way that a ''propeller-like'' molecule with screw-type chirality results. Crystals of 4 are triclinic, space group P1, with unit cell dimensions a = 11.411(4) A, b = 13.325(4) Angstrom, c = 13.599(4) Angstrom, alpha = 88.91(3)degrees, beta = 65.44(2)degrees, gamma = 72.77(3)degrees, and Z = 1. In 4 the chlorine,the two yttrium and the sodium atoms lie on a pseudo-3-fold axis (Cl-Y(1)... Y(2)... Na: angle Cl-Y ... Y = 179.36(8)degrees and angle Y ... Y ... Na = 178.38(10)degrees) around which the six phenolate ligands are arranged in two shells of three ligands. One shell bridges the yttrium atoms in an asymmetric fashion, while the second shell bridges the second yttrium and the sodium atom, resulting in two shells of opposite screw-type chirality. H-1, C-13, and Y-89 (for 3b and 4) NMR confirmed that the structures found for 3a and 4 in the solid state are retained in solution. For 4 Y-89 NMR showed two separate resonances (202.4 and 132.4 ppm), with (2)J(YY) = 0.4 HZ. The formation of 3a and 3b is described as resulting from positive cooperativity ih anion-cation bonding: coordination of chloride anion to a neutral metal tris(phenolate) leads to preorganization of available binding sites in the resulting anionic complex for the binding of the sodium cation. In 4 this cooperativity is the driving force for the self-assembly of an anionic bimetallic molecular structure with available, preorganized binding sites for the capture of the cation. A proposal is made to use these observations for the possible synthesis of new coordination polymers.
引用
收藏
页码:1185 / 1194
页数:10
相关论文
共 69 条
  • [1] OXYGENATION OF CYCLOPALLADATED N,N-DIMETHYLBENZYLAMINE COMPLEXES BY INORGANIC AND ORGANIC PEROXIDES - OXYGEN INSERTION INTO THE PALLADIUM-CARBON BOND
    ALSTERS, PL
    TEUNISSEN, HT
    BOERSMA, J
    SPEK, AL
    VANKOTEN, G
    [J]. ORGANOMETALLICS, 1993, 12 (11) : 4691 - 4696
  • [2] COMPLETION AND REFINEMENT OF CRYSTAL-STRUCTURES WITH SIR92
    ALTOMARE, A
    CASCARANO, G
    GIACOVAZZO, C
    GUAGLIARDI, A
    [J]. JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1993, 26 (pt 3) : 343 - 350
  • [3] SYNTHESIS, PROPERTIES, AND X-RAY STRUCTURES OF THE LANTHANIDE ETA-6-ARENE-BRIDGED ARYLOXIDE DIMERS LN2(O-2,6-I-PR2C6H3)6 AND THEIR LEWIS BASE ADDUCTS LN(O-2,6-I-PR2C6H3)3(THF)2 (LN=PR, ND, SM, GD, ER, YB, LU)
    BARNHART, DM
    CLARK, DL
    GORDON, JC
    HUFFMAN, JC
    VINCENT, RL
    WATKIN, JG
    ZWICK, BD
    [J]. INORGANIC CHEMISTRY, 1994, 33 (16) : 3487 - 3497
  • [4] BEURSKENS PT, 1992, DIRDIF PROGRAM SYSTE
  • [5] SYNTHESIS AND CHARACTERIZATION OF NOVEL YTTRIUM COPPER ALKOXIDE CLUSTERS
    BIDELL, W
    DORING, J
    BOSCH, HW
    HUND, HU
    PLAPPERT, E
    BERKE, H
    [J]. INORGANIC CHEMISTRY, 1993, 32 (05) : 502 - 507
  • [6] HETEROMETALLIC COMPOUNDS INVOLVING D-BLOCK AND F-BLOCK ELEMENTS - SYNTHESIS, STRUCTURE, AND MAGNETIC-PROPERTIES OF 2 NEW LNXCU4 COMPLEXES
    BLAKE, AJ
    MILNE, PEY
    THORNTON, P
    WINPENNY, REP
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1991, 30 (09): : 1139 - 1141
  • [7] Bradley D.C., 1978, METAL ALKOXIDES
  • [8] VOLATILE TRIS-TERTIARY-ALKOXIDES OF YTTRIUM AND LANTHANUM - THE X-RAY CRYSTAL-STRUCTURE OF [LA3(OBU-TERT)9(BU-TERTOH)2]
    BRADLEY, DC
    CHUDZYNSKA, H
    HURSTHOUSE, MB
    MOTEVALLI, M
    [J]. POLYHEDRON, 1991, 10 (10) : 1049 - 1059
  • [9] METAL ALKOXIDES AS PRECURSORS FOR ELECTRONIC AND CERAMIC MATERIALS
    BRADLEY, DC
    [J]. CHEMICAL REVIEWS, 1989, 89 (06) : 1317 - 1322
  • [10] BRINKER CJ, 1986, MATER RES SOC S P, P73