LIGAND-FIELD STRENGTHS AND OXIDATION-STATES FROM MANGANESE L-EDGE SPECTROSCOPY

被引:208
作者
CRAMER, SP
DEGROOT, FMF
MA, Y
CHEN, CT
SETTE, F
KIPKE, CA
EICHHORN, DM
CHAN, MK
ARMSTRONG, WH
LIBBY, E
CHRISTOU, G
BROOKER, S
MCKEE, V
MULLINS, OC
FUGGLE, JC
机构
[1] AT&T BELL LABS,MURRAY HILL,NJ 07974
[2] INDIANA UNIV,DEPT CHEM,BLOOMINGTON,IN 47405
[3] CATHOLIC UNIV NIJMEGEN,MAT RES INST,6525 ED NIJMEGEN,NETHERLANDS
[4] SCHLUMBERGER DOLL RES CTR,RIDGEFIELD,CT 06877
[5] UNIV CALIF BERKELEY,DEPT CHEM,BERKELEY,CA 94720
[6] UNIV CANTERBURY,DEPT CHEM,CHRISTCHURCH 1,NEW ZEALAND
[7] UNIV CALIF BERKELEY LAWRENCE BERKELEY LAB,DIV APPL CHEM,BERKELEY,CA 94720
关键词
D O I
10.1021/ja00021a018
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
L2,3 X-ray absorption spectra have been recorded for Mn(II), Mn(III), and Mn(IV) samples with a variety of ligands. For high-spin Mn(II) complexes, a systematic variation in spectra is observed as the ligand field is increased. A dramatically different spectrum is observed for Mn(CN)6(4-), consistent with the presence of a low-spin complex. Progressing in oxidation state from Mn(II) to Mn(III) through Mn(IV) complexes, the primary peak position shifts first 1.5-2 eV and then 1-2 eV to higher energy, and the ratio of L3 to L2 intensity decreases. The spectra have been quantitatively simulated with an atomic multiplet program with an octahedral crystal field superimposed. The high resolution, strong sensitivity to chemical environment and amenability to quantitative spectral shape analysis indicate that L-edges of the first transition series metals are a potentially useful probe for bioinorganic studies.
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页码:7937 / 7940
页数:4
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