PREPARATION AND X-RAY STRUCTURES OF K[LN(O-2,6-I-PR2C6H3)4] (LN=LA, ND, ER) - EXTENDED-CHAIN STRUCTURES OF LANTHANIDE TETRAKIS(ARYLOXIDE) ANIONS BRIDGED BY POTASSIUM-ETA-ARENE INTERACTIONS

被引:89
作者
CLARK, DL
GORDON, JC
HUFFMAN, JC
VINCENTHOLLIS, RL
WATKIN, JG
ZWICK, BD
机构
[1] LOS ALAMOS NATL LAB,DIV NUCL MAT TECHNOL,LOS ALAMOS,NM 87545
[2] INDIANA UNIV,CTR MOLEC STRUCT,DEPT CHEM,BLOOMINGTON,IN 47405
关键词
D O I
10.1021/ic00103a044
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of several lanthanide trichlorides LnCl(3) (Ln = La, Nd, Er, Lu) with 3 or 4 equiv of potassium 2,6-diisopropylphenoxide in THF solution leads to the formation of potassium salts of formula K[Ln(O-2,6-i-Pr2C6H3)(4)] [Ln = Nd (5), Er (6), Lu (7), La(8)]. These salts exhibit unusual solid-state structures involving multihapto potassium-pi-arene interactions. Not all lanthanide trichlorides produce the potassium salt directly from this reaction, and the nature of the product appears to be related to the solubility of the LnCl(3) starting material in THF solution. Compounds 5 and 6 exist in the solid state as pseudo-one-dimensional infinite-chain structures featuring multihapto K-C interactions with phenyl rings from two adjacent [Ln(OAr)(4)](-) units. Compound 8 forms a pseudo-two-dimensional sheet structure, with multihapto K-C interactions linking three neighboring [Ln(OAr)(4)](-) units. Ln-O distances within the tetrahedral [Ln(OAr)(4)](-) units average 2.211(12) (5), 2.084(14) (6) and 2.253(6) Angstrom (8). Potassium-carbon distances of the arene rings are in the ranges 3.097(8)-3.772(11) Angstrom (5), 3.018(8)-3.484(10) Angstrom (6) and 3.089(3)-3.519(4) Angstrom (8). Crystal data for 5 (at -171 degrees C): monoclinic space group P2(1)/n, a = 12.990(4) Angstrom, b = 18.977(6) Angstrom, c = 18.594(5) Angstrom, beta = 93.94(1)degrees, V = 4572.66 Angstrom(3), d(calc) = 1.296 g cm(-3), Z = 4, R = 0.0538, R(W) = 0.0530. Crystal data for 6 (at -161 degrees C): monoclinic space group P2(1)/n, a = 10.567(3) Angstrom, b = 20.856(6) Angstrom, c = 20.938(6) Angstrom, beta = 102.72(1)degrees V = 4500.93 Angstrom(3), d(calc) = 1.351 g cm(-3), Z = 4, R = 0.0362, R(W) = 0.0368. Crystal data for 8 (at -171 degrees C): orthorhombic space group Pcab, a = 19.153(2) Angstrom, b = 20.898(3) Angstrom, c = 22.673(3) Angstrom, V = 9074.66 Angstrom(3), d(calc) = 1.299 g cm(-3), Z = 8, R = 0.0272, R(W) = 0.0281.
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页码:5903 / 5911
页数:9
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