THE SYNTHESIS AND PROPERTIES OF AN ENCAPSULATED RUTHENIUM(II) ION BY AN N3S3 MACROBICYCLIC LIGAND

被引：12
作者：
BERNHARD, P
BULL, DJ
ROBINSON, WT
SARGESON, AM
机构：
[1] AUSTRALIAN NATL UNIV,RES SCH CHEM,CANBERRA,ACT 2601,AUSTRALIA
[2] UNIV CANTERBURY,DEPT CHEM,CHRISTCHURCH 1,NEW ZEALAND
来源：
AUSTRALIAN JOURNAL OF CHEMISTRY | 1992年 / 45卷 / 08期
关键词：
D O I：
10.1071/CH9921241
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The complex [Ru(capten)]2+ (capten = 1-methyl-3,13,16-trithia-6,10,19-triazabicyclo[6.6.6]-icosane) has been synthesized from [Ru(dmf)6]2+ (dmf = N,N-dimethylformamide) and the free ligand. An X-ray crystallographic analysis of [Ru(capten)] (CF3SO3)2 at 138 K reveals a lel3 conformation of the ligand with an average R(II)-N bond length of 2.136(5) angstrom and an average Ru(II)-S bond length of 2.284(8) angstrom. Visible spectra and the redox potential (1.26 V v. n.h.e.) show that the Ru(II) state is stabilized by c. 0.9 V relative to the complex with six nitrogen donor atoms. Oxidation of Ru(II) to Ru(III) in acetonitrile leads to dehydrogenation of the ligand to form an imine. Successive oxidations lead to a triimine species where all the imines are located in the ligand cap. These oxidation processes are inferred to take place through Ru(IV) intermediates which decay by intramolecular 2e- steps to the imine.
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页码：1241 / 1254
页数：14
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