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  • Variation of electronic transitions and reduction potentials of cerium(IV) complexes.

Variation of electronic transitions and reduction potentials of cerium(IV) complexes.

Dalton transactions (Cambridge, England : 2003) (2014-08-26)
Ursula J Williams, David Schneider, Walter L Dorfner, Cäcilia Maichle-Mössmer, Patrick J Carroll, Reiner Anwander, Eric J Schelter
ABSTRACT

The trivalent compound K[Ce[N(SiHMe2)2]4] was synthesized and oxidized, providing a convenient route to the reported cerium(IV) compound Ce[N(SiHMe2)2]4. Protonolysis reactions of Ce[N(SiHMe2)2]4 with tert-butanol, substituted benzyl alcohols, and 2,6-diphenylphenol yielded the neutral tetravalent compounds Ce(O(t)Bu)4(py)2, Ce2(OCH2C6R5)8(thf)2 (R = Me, F), and Ce(Odpp)4 (dpp = 2,6-(C6H5)2-C6H3). Spectroscopic and electrochemical characterization of the monometallic cerium(IV) silylamide, alkoxide, and aryloxide compounds revealed variable ligand-to-metal charge transfer transitions and metal-based reduction potentials. Computational bonding analyses were performed to complement the physical characterization of the complexes.

MATERIALS
Product Number
Brand
Product Description

Supelco
Diethyl ether, analytical standard
Sigma-Aldrich
Diethyl ether, contains 1 ppm BHT as inhibitor, anhydrous, ≥99.7%
Sigma-Aldrich
Diethyl ether
Sigma-Aldrich
Diethyl ether, suitable for HPLC, ≥99.9%, inhibitor-free
Sigma-Aldrich
Diethyl ether, ACS reagent, ≥98.0%, contains ≤2% ethanol and ≤10ppm BHT as inhibitor
Sigma-Aldrich
Diethyl ether, reagent grade, ≥98%, contains ≤2% ethanol and ≤10ppm BHT as inhibitor
Sigma-Aldrich
Diethyl ether, anhydrous, ACS reagent, ≥99.0%, contains BHT as inhibitor
Sigma-Aldrich
Diethyl ether, contains BHT as inhibitor, puriss. p.a., ACS reagent, reag. ISO, reag. Ph. Eur., ≥99.8% (GC)
Sigma-Aldrich
Diethyl ether, puriss., contains ~5 mg/L 2,6-di-tert.-butyl-4-methylphenol as stabilizer, meets analytical specification of Ph. Eur., BP, ≥99.5% (GC)
Sigma-Aldrich
Diethyl ether, ACS reagent, anhydrous, ≥99.0%, contains BHT as inhibitor
Supelco
Dichloromethane, Selectophore, ≥99.5%
Sigma-Aldrich
Pentane, anhydrous, ≥99%
Sigma-Aldrich
Dichloromethane, anhydrous, ≥99.8%, contains 40-150 ppm amylene as stabilizer
Sigma-Aldrich
Benzene-D6, 99 atom % D
Sigma-Aldrich
Pyridine, anhydrous, 99.8%
Sigma-Aldrich
2,6-Diphenylphenol, 98%
Sigma-Aldrich
Dichloromethane, suitable for HPLC, ≥99.9%, contains 40-150 ppm amylene as stabilizer
Sigma-Aldrich
Ferrocene, 98%
Supelco
Dichloromethane, analytical standard
Supelco
Hexane, analytical standard
Supelco
Toluene, analytical standard
Supelco
Pentane, analytical standard
Supelco
Pyridine, analytical standard
Sigma-Aldrich
Benzene-D6, "100%", 99.96 atom % D
Sigma-Aldrich
Benzene-D6, 99.6 atom % D
Sigma-Aldrich
Benzene-D6, 99.6 atom % D, contains 0.03 % (v/v) TMS
Sigma-Aldrich
Benzene-D6, anhydrous, ≥99.6 atom % D
Sigma-Aldrich
Toluene, anhydrous, 99.8%
Supelco
tert-Butanol, analytical standard
Sigma-Aldrich
Pyridine, ≥99%