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Title: Multi‐electron Oxidation of Ce(III) Complexes Facilitated by Redox‐Active Ligands

Journal Article · · European Journal of Inorganic Chemistry
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  1. H.C. Brown Department of Chemistry Purdue University West Lafayette Indiana 47907 USA
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Abstract A family of cerium complexes featuring a redox‐active ligand in different oxidation states has been synthesized, including the the iminosemiquinone (isq) 1− compound, Ce( dipp isq) 3 ( 1‐Ceisq ), and the amidophenolate (ap) 2− species Ce III ( dipp ap) 3 K 3 ( 2‐Ceap ), [Ce III ( dipp ap) 3 K][K(18‐c‐6)] 2 ( 2‐Ceap 18c6 ), and [Ce III ( dipp ap) 3 K][K(15‐c‐5) 2 ] 2 ( 2‐Ceap 15c5 ). Treating 2‐Ceap 15c5 with dioxogen furnishes the cerium(IV) derivative [Ce IV ( dipp ap) 3 ][K(15‐c‐5) 2 ] 2 ( 3‐Ceap 15c5 ), and an analogous synthesis can be used to generate [Ce IV ( dipp ap) 3 ][K(crypt)] 2 ( 3‐Ceap crypt ). Similarly, addition of hexamethyldisiloxane produces an interesting bis(amidophenolate) species, [(Me 3 SiO) 2 Ce IV ( dipp ap) 2 ][K(15‐c‐5) 2 ] 2 ( 4‐CeOSiMe 3 ). Full spectroscopic and structural characterization of each derivative was performed to establish the oxidation states of both the ligands and the cerium ions.

Sponsoring Organization:
USDOE
Grant/Contract Number:
NONE; SC0008479
OSTI ID:
2324673
Journal Information:
European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry; ISSN 1434-1948
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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