Ligand field stabilization energies of the hexaaqua 3+complexes of the first transition series

被引:27
作者
Johnson, DA [1 ]
Nelson, PG
机构
[1] Open Univ, Dept Chem, Milton Keynes MK7 6AA, Bucks, England
[2] Univ Hull, Dept Chem, Hull HU6 7RX, N Humberside, England
关键词
D O I
10.1021/ic990426i
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
An analysis of the ligand field stabilization energy which makes allowance for the nephelauxetic effect is shown to give satisfactory results when applied to the hydration enthalpies of the hexaaqua 3+ complexes of the first transition series. The contribution from the nephelauxetic effect is substantial, and the baseline for zero ligand field stabilization energy is displaced below the d(0) point. In these respects, the complexes show a closer resemblance to the hexafluorometalates(III) than to the hexaaqua 2+ ions. Ln the course of the analysis, the electronic spectra of the cesium alums of vanadium(III), manganese(III), and cobalt(III) are reexamined, and thermodynamic properties of particular complexes are calculated. These include Delta H-f(circle minus)(Ti3+, aq), E-circle minus(Ti3+\Ti2+), and the relative stabilities of the high- and low-spin states of Co3+(aq), Mn3+(aq), and Cr2+(aq). The general influence of ligand field stabilization energies on redox potentials is also discussed.
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收藏
页码:4949 / 4955
页数:7
相关论文
共 59 条
[21]  
GEORGE P, 1959, PROGR INORG CHEM, V1, P381
[22]  
GRATZEL M, 1985, INORG CHEM, V24, P2320
[23]   THE CRYSTAL STRUCTURES OF THE TRIFLUORIDES OF IRON, COBALT, RUTHENIUM, RHODIUM, PALLADIUM AND IRIDIUM [J].
HEPWORTH, MA ;
JACK, KH ;
PEACOCK, RD ;
WESTLAND, GJ .
ACTA CRYSTALLOGRAPHICA, 1957, 10 (01) :63-69
[24]  
HILL JO, 1971, CHEM REV, V71, P127
[25]   THERMOCHEMISTRY OF INORGANIC SOLIDS .7. EMPIRICAL RELATIONS AMONG ENTHALPIES OF FORMATION OF HALIDES [J].
HISHAM, MWM ;
BENSON, SW .
JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (13) :3631-3637
[27]   ELECTRONIC-SPECTRUM AND METAL-LIGAND BONDING PARAMETERS OF THE V(H2O)63+ ION [J].
HITCHMAN, MA ;
MCDONALD, RG ;
SMITH, PW ;
STRANGER, R .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1988, (05) :1393-1395
[28]   AQUO COMPLEXES OF METAL-IONS [J].
HUNT, JP ;
FRIEDMAN, HL .
PROGRESS IN INORGANIC CHEMISTRY, 1983, 30 :359-387
[29]   FACTORS DETERMINING THE LIGAND-FIELD STABILIZATION ENERGIES OF THE HEXAAQUA-2+ COMPLEXES OF THE FIRST TRANSITION SERIES AND THE IRVING-WILLIAMS ORDER [J].
JOHNSON, DA ;
NELSON, PG .
INORGANIC CHEMISTRY, 1995, 34 (22) :5666-5671
[30]   THERMODYNAMIC PROPERTIES OF CO3+(AQ) [J].
JOHNSON, DA ;
NELSON, PG .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1990, (01) :1-4