STRUCTURE AND MIXED-VALENCE STATES OF THE TRINUCLEAR IRON(II,III,III) PIVALATE COMPLEX-PIVALIC ACID ADDUCT, [FE3O(O(2)CCME(3))(6)(ME(3)CCO(2)H)(3)](ME=-CH3)

被引:27
作者
ASAMAKI, K
NAKAMOTO, T
KAWATA, S
SANO, H
KATADA, M
ENDO, K
机构
[1] TOKYO METROPOLITAN UNIV, FAC SCI, DEPT CHEM, HACHIOJI, TOKYO 19203, JAPAN
[2] TOKYO METROPOLITAN UNIV, RADIOISOTOPE RES CTR, HACHIOJI, TOKYO 19203, JAPAN
[3] SHOWA COLL PHARMACEUT SCI, MACHIDA, TOKYO 194, JAPAN
关键词
CRYSTAL STRUCTURES; IRON COMPLEXES; PIVALATE COMPLEXES; PIVALIC ACID COMPLEXES; TRINUCLEAR COMPLEXES; MOSSBAUER SPECTRA;
D O I
10.1016/0020-1693(95)04639-Q
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The structure of the mixed-valence trinuclear iron pivalate complex-pivalic acid adduct, [Fe3O(O(2)CCMe(3))(6)( Me(3)CCO(2)H)(3)] (Me = -CH3), was characterized by single crystal X-ray diffraction. The adduct crystallizes in the orthorhombic system, space group Cmcm, with a = 18.437(1), b = 20.339(2), c = 17.171(1) Angstrom, V = 6456(1) Angstrom(3) and Z = 4, without solvate molecules of crystallization. The adduct is first characterized to be a mixed-valence Fe3O compound with carboxylic acid coordinating to the iron atom. The acid is coordinated through the carbonyl O atom trans to the mu(3)-oxo atom, disordered for crystallographic mirror symmetry. Although there are two crystallographically non-equivalent iron sites, no significant difference is seen between their coordination environments at room temperature. The complex shows a valence-trapped state below similar to 100 K and a valence-detrapped state above similar to 230 K up to room temperature on the Fe-57 Mossbauer time-scale (similar to 10(-7)-10(-8) s), whereas it shows an evidence of valence trapping on the IR time-scale (similar to 10(-12)-10(-13) s) at room temperature. The temperature-dependent valence transformation is found to culminate with a first-order phase transition at similar to 230 K.
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页码:155 / 161
页数:7
相关论文
共 28 条
[1]   REACTIONS OF TITANIUM TETRACHLORIDE WITH CARBOXYLIC-ACIDS - CRYSTAL AND MOLECULAR-STRUCTURE OF THE DINUCLEAR TITANIUM OXO COMPOUND [(TICL2(O(2)CBU(T))(BU(T)CO(2)H))O-2] [J].
BARROW, H ;
BROWN, DA ;
ALCOCK, NW ;
CLASE, HJ ;
WALLBRIDGE, MGH .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1994, (02) :195-199
[2]   CRYSTAL-STRUCTURE AND MASS-SPECTRUM OF MU3-OXO-HEXAKIS(MU-TRIMETHYL-ACETATO)-TRISMETHANOLTRI-IRON(III) CHLORIDE, A TRINUCLEAR BASIS IRON(III) CARBOXYLATE [J].
BLAKE, AB ;
FRASER, LR .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1975, (03) :193-197
[3]   SIR88 - A DIRECT-METHODS PROGRAM FOR THE AUTOMATIC SOLUTION OF CRYSTAL-STRUCTURES [J].
BURLA, MC ;
CAMALLI, M ;
CASCARANO, G ;
GIACOVAZZO, C ;
POLIDORI, G ;
SPAGNA, R ;
VITERBO, D .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1989, 22 :389-393
[4]   CHEMICAL AND PHYSICAL-PROPERTIES OF TRIANGULAR BRIDGED METAL-COMPLEXES [J].
CANNON, RD ;
WHITE, RP .
PROGRESS IN INORGANIC CHEMISTRY, 1988, 36 :195-298
[5]   MAGNETIC AND SPECTROSCOPIC PROPERTIES OF FEIIFEIII2O(CH3CO2)6L3, L = H2O OR C5H5N - DIRECT OBSERVATION OF THE THERMAL BARRIER TO ELECTRON-TRANSFER IN A MIXED-VALENCE COMPLEX [J].
DZIOBKOWSKI, CT ;
WROBLESKI, JT ;
BROWN, DB .
INORGANIC CHEMISTRY, 1981, 20 (03) :679-684
[6]  
GERBELEU NV, 1986, ZH NEORG KHIM+, V31, P684
[7]  
GERBELEU NV, 1986, RUSS J INORG CHEM, V31, P390
[8]  
GOLDANSKII VI, 1973, DOKL AKAD NAUK SSSR+, V213, P867
[9]  
GOLDANSKII VI, 1973, DOKL AKAD NAUK, V213, P1063
[10]   EFFECT OF QUENCHED DISORDER ON PHASE-TRANSITIONS IN THE MIXED-VALENCE SOLID-SOLUTION [FE-III2FE-II1-XCO-IIXO(O2CCH3)6(PY)3](PY) [J].
JANG, HG ;
KAJI, K ;
SORAI, M ;
WITTEBORT, RJ ;
GEIB, SJ ;
RHEINGOLD, AL ;
HENDRICKSON, DN .
INORGANIC CHEMISTRY, 1990, 29 (18) :3547-3556