ISSN:
1434-1948
Keywords:
Thiolato-bridged complexes
;
Iron
;
Ruthenium
;
Mixed-valent compounds
;
Mössbauer spectroscopy
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of [FeIIIL] with [RuIICl2(dmso)4] in methanol under argon, affords, upon addition of NaPF6, brown crystals of [LFeRuFeL](PF6)2· 3 CH3OH (1). Its one-electron oxidation product [LFeRuFeL](PF6)3 (2) [L = 1,4,7-(4-tert-butyl-2-mercaptobenzyl)-1,4,7-triazacyclononane] was generated by using one equivalent of [NO]BF4. The crystal structure determination of [LFeRuFeL](BPh4)2· CH3CN · 3 (CH3)2CO shows that 1 contains a trinuclear, face-sharing thiolato-bridged dication. Mössbauer spectroscopy established that the oxidation state distribution of 1 can best be described by Fe2.5RuIIIFe2.5 and 2 by FeIIIRuIIIFeIII. Complex 1 possesses a diamagnetic (St = 0) and 2 an St = 1/2 ground state. The electronic structures of 1 and 2 are rationalized by an MO picture involving Fe-Ru metal-metal bonds of bond order 0.5 in both species. Complex 1 is formally a mixed valence compound with complete delocalization of the “excess electron” (class III).
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
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