STABILIZATION OF COBALT CAGE CONFORMERS IN THE SOLID-STATE AND SOLUTION

被引:36
作者
BERNHARDT, PV [1 ]
BYGOTT, AMT [1 ]
GEUE, RJ [1 ]
HENDRY, AJ [1 ]
KORYBUTDASZKIEWICZ, BR [1 ]
LAY, PA [1 ]
PLADZIEWICZ, JR [1 ]
SARGESON, AM [1 ]
WILLIS, AC [1 ]
机构
[1] UNIV SYDNEY,SCH CHEM,DIV INORGAN CHEM,SYDNEY,NSW 2006,AUSTRALIA
关键词
D O I
10.1021/ic00098a023
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The cage complexes [Co{(NMe(2))(2)sar}](3+) and [Co{(NMe(2),Me)sar}](3+) (sar = sarcophagine = 3,6,10,13,16,19 hexaazabicyclo[6.6.6]icosane; (NMe(2))(2)sar 1,8-bis(dimethylamino)sarcophagine; (NMe(2),Me)sar 1-(dimethylamino)-8-methylsarcophagine) are obtained by methylation of amino substituents on the parent cage complexes using formaldehyde and formic acid. Further methylation with methyl iodide in dimethyl sulfoxide, or with dimethyl sulfate in N,N-dimethylformamide, converts the dimethylamino substituents to trimethylammonium substituents and essentially inverts the circular dichroism (CD) spectrum in comparison to that of the protonated parent cage complex, [Co{(NH3)(2)sar}](5+). A combination of NMR and electronic spectroscopic measurements indicates that the inversion of the CD spectra is due to conformational inversions in the 1,2-ethanediamine rings from mainly a lel conformation in [Co{(NH3)(3)sar}](5+) to an obs conformation in [Co{(NMe(3))(2)sar}](5+), (without inversion at any of the seven stereogenic centers; Co plus six coordinated amines). This ob(3) conformation was identified in the solid state by an X-ray crystallographic analysis of [Co{(NMe(3))(2)sar}](NO3)(5).3H(2)O: monoclinic, P2(1)/n, a 14.382(4) Angstrom, b = 14.604(3) Angstrom, c 16.998(6) Angstrom, beta = 100.28(3)degrees, Z= 4. The electron self-exchange rate constant of the [Co((NMe(3))2sar)](5+/4+) redox couple (+0.05 V vs NHE, 0.011(1) M(-1) s(-1) at 25 degrees C, I = 0.2 M (NaCl)) is a factor of 2 smaller than that of the [Co((NH3)2sar)](5+/4+) couple under the same conditions and is the slowest electron-transfer rate so far measured for a hexaamine cage complex of this type. However, it is still much faster than those of the parent [Co(en)(3)](3+/2+) and [Co(NH3)(6)](3+/2+) couples. This paper also provides hard evidence for the conformations of other Co(III) cage complexes in solution as well as the solid state.
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页码:4553 / 4561
页数:9
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共 46 条
[1]   KINETICS OF THE SUPEROXIDE RADICAL OXIDATION OF [COBALT SEPULCHRATE](2+) - A FLASH PHOTOLYTIC STUDY [J].
BAKAC, A ;
ESPENSON, JH ;
CREASER, II ;
SARGESON, AM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (26) :7624-7628
[2]   KINETICS OF THE REDUCTION OF NITRO TO HYDROXYLAMINE GROUPS BY DITHIONITE IN A COBALT(II) CRYPTAND COMPLEX - X-RAY-ANALYSIS OF [1,8-BIS(HYDROXYAMINO)-3,6,10,13,16,19-HEXAAZABICYCLO[6.6.6]EICOSANE]COBALT(III) CHLORIDE TETRAHYDRATE [J].
BALAHURA, RJ ;
FERGUSON, G ;
RUHL, BL ;
WILKINS, RG .
INORGANIC CHEMISTRY, 1983, 22 (26) :3990-3992
[3]   STEPWISE DEHYDROGENATION OF A RU(III) HEXAAMINE CAGE COMPLEX TO A HEXAIMINE RU(II) COMPLEX VIA RU(IV) INTERMEDIATES [J].
BERNHARD, P ;
SARGESON, AM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (02) :597-606
[4]   ELECTRON-TRANSFER REACTIONS OF ENCAPSULATED RUTHENIUM, MANGANESE, IRON, AND NICKEL - SELF-EXCHANGE RATES FOR (3,6,10,13,16,19-HEXAAZABICYCLO[6.6.6]EICOSANE)METAL(3+/2+) COUPLES [J].
BERNHARD, P ;
SARGESON, AM .
INORGANIC CHEMISTRY, 1987, 26 (24) :4122-4125
[5]   ELECTROCHEMISTRY OF MACROBICYCLIC (HEXAAMINE)COBALT(III) COMPLEXES - METAL-CENTERED AND SUBSTITUENT REDUCTIONS [J].
BOND, AM ;
LAWRANCE, GA ;
LAY, PA ;
SARGESON, AM .
INORGANIC CHEMISTRY, 1983, 22 (14) :2010-2021
[6]   STRUCTURAL CHARACTERIZATION OF ENCAPSULATION REACTIONS BASED ON THE TRIS(ETHANE-1,2-DIAMINE)COBALT(III) ION [J].
CLARK, IJ ;
GEUE, RJ ;
ENGELHARDT, LM ;
HARROWFIELD, JM ;
SARGESON, AM ;
WHITE, AH .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1993, 46 (10) :1485-1505
[7]   ANALYSIS OF TRIGONAL-PRISMATIC AND OCTAHEDRAL PREFERENCES IN HEXAAMINE CAGE COMPLEXES [J].
COMBA, P ;
SARGESON, AM ;
ENGELHARDT, LM ;
HARROWFIELD, JM ;
WHITE, AH ;
HORN, E ;
SNOW, MR .
INORGANIC CHEMISTRY, 1985, 24 (15) :2325-2327
[8]   OUTER-SPHERE ELECTRON-TRANSFER REACTIONS INVOLVING CAGED COBALT IONS [J].
CREASER, II ;
SARGESON, AM ;
ZANELLA, AW .
INORGANIC CHEMISTRY, 1983, 22 (26) :4022-4029
[9]   SYNTHESIS AND REACTIVITY OF AZA-CAPPED ENCAPSULATED CO(III) IONS [J].
CREASER, II ;
GEUE, RJ ;
HARROWFIELD, JM ;
HERLT, AJ ;
SARGESON, AM ;
SNOW, MR ;
SPRINGBORG, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (22) :6016-6025
[10]   ENERGY-TRANSFER VS ELECTRON-TRANSFER IN THE EXCITED-STATE QUENCHING OF TRIS(2,2'-BIPYRIDINE-N,N')RUTHENIUM(II) COMPLEXES BY COBALT(III) CAGE COMPLEXES - APPLICATIONS TO THE PHOTOREDUCTION OF WATER [J].
CREASER, II ;
GAHAN, LR ;
GEUE, RJ ;
LAUNIKONIS, A ;
LAY, PA ;
LYDON, JD ;
MCCARTHY, MG ;
MAU, AWH ;
SARGESON, AM ;
SASSE, WHF .
INORGANIC CHEMISTRY, 1985, 24 (17) :2671-2680