
TY  - JOUR
A1  - Bernhard, P 
A1  - Bull, DJ 
A1  - Robinson, WT 
A1  - Sargeson, AM 
T1  - The Synthesis and Properties of an Encapsulated Ruthenium(II) Ion by an N<sub>3</sub>S<sub>3</sub> Macrobicyclic Ligand
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1992
VL  - 45
IS  - 8
SP  - 1241
EP  - 1254
KW  - 
UR  - https://doi.org/10.1071/CH9921241 
N2  - 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 II-N bond length of 2.136(5) Å and an average RuII-S bond length of 2.284(8) Å . Visible spectra and the redox potential (1.26 V v. n.h.e .) show that the RuII state is stabilized by c. 0.9 V relative to the complex with six nitrogen donor atoms. Oxidation of Ru11 to RuIIIin 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 RuIV  intermediates which decay by intramolecular 2e- steps to the imine. 
ER  -

