Irradiation of L_OEtRuCl₂(NO) (L_OEt^- = [CpCo{P(O)(OEt)₂}₃]^- where Cp = η⁵-C₅H₅) with UV light in CH₂Cl₂/CH₃CN afforded the Ru(III) solvato complex L_OEtRuCl₂(CH₃CN). Similarly, photolysis of L_OEtRuCl₂(NO) in tetrahydrofuran (THF)/H₂O, followed by silica gel chromatography yielded [L_OEtRuCl]₂(μ-Cl)₂. Refluxing L_OEtRuCl₂(CH₃CN) with RNH₂ in THF afforded L_OEtRuCl₂(NH₂R) (R = t-Bu, p-tol and Ph). Reaction of RuCl₃(N^N)(NO) with AgL_OEt and AgOTf (OTf- = triflate) afforded [L_OEtRu(N^N)(NO)][OTf]₂ where N^N = 4,4’-di-tert-butyl-2,2’-bipyridyl (dtbpy), 2,2’-bipyridyl (bpy) and N,N,N',N'-tetramethylethylenediamine (tmeda). Photolysis of [L_OEtRu(dtbpy)(NO)][OTf]₂ in CH₂Cl₂/CH₃CN afforded [L_OEtRu(dtbpy)CH₃CN][OTf]₂. Treatment of [L_OEtRu(bpy)(NO)][BF₄]₂ with benzyl amine led to formation of [{L_OEtRu(...[ Read more ]

Irradiation of L_OEtRuCl₂(NO) (L_OEt^- = [CpCo{P(O)(OEt)₂}₃]^- where Cp = η⁵-C₅H₅) with UV light in CH₂Cl₂/CH₃CN afforded the Ru(III) solvato complex L_OEtRuCl₂(CH₃CN). Similarly, photolysis of L_OEtRuCl₂(NO) in tetrahydrofuran (THF)/H₂O, followed by silica gel chromatography yielded [L_OEtRuCl]₂(μ-Cl)₂. Refluxing L_OEtRuCl₂(CH₃CN) with RNH₂ in THF afforded L_OEtRuCl₂(NH₂R) (R = t-Bu, p-tol and Ph). Reaction of RuCl₃(N^N)(NO) with AgL_OEt and AgOTf (OTf- = triflate) afforded [L_OEtRu(N^N)(NO)][OTf]₂ where N^N = 4,4’-di-tert-butyl-2,2’-bipyridyl (dtbpy), 2,2’-bipyridyl (bpy) and N,N,N',N'-tetramethylethylenediamine (tmeda). Photolysis of [L_OEtRu(dtbpy)(NO)][OTf]₂ in CH₂Cl₂/CH₃CN afforded [L_OEtRu(dtbpy)CH₃CN][OTf]₂. Treatment of [L_OEtRu(bpy)(NO)][BF₄]₂ with benzyl amine led to formation of [{L_OEtRu(bpy)}₂(μ-N₂)][BF₄]₂ that exhibited ν(N≡N) at ca. 2009 cm^-1 in the Raman spectrum. Oxidation of [{L_OEtRu(bpy)}₂(μ-N₂)][BF₄]₂ with [Cp₂Fe][BF₄] afforded the Ru(III)/Ru(II) mixed valence complex [{L_OEtRu(bpy)}₂(μ-N₂)][BF₄]₃ that showed an intervalence charge transfer band at 1893 nm. The reduction potentials of the above Ru-L_OEt complexes have been determined by cyclic voltammetry.

Reduction of [L_OEtRuCl]₂(μ-Cl)₂ with zinc granule in CH₃CN, followed by treatment with NH₄PF₆ gave [L_OEtRu(CH₃CN)₃][PF₆]. Reduction of [L_OEtRuCl]₂(μ-Cl)₂ with zinc granule in CH₃OH under nitrogen afforded a Ru(II) terminal dinitrogen complex, which was converted to the heterometallic Ru(II)/Zn(II) methoxide cluster (L_OEtRu)₂Zn₂(μ₂-OCH₃)₄(μ₃-OCH₃)₂(CH₃OH)₂ upon recrystallization from acetone in air. This Ru(II) dinitrogen complex can catalyze the C=C double bond isomerization of terminal olefins such as hex-1-ene, hex-5-en-1-ol and allyl phenyl ether.

Reaction of L_OEtRu(N)Cl₂ with PCy₃ afforded L_OEtRuCl₂(NPCy₃) (Cy = cyclohexyl), which can be oxidized by tris(4-bromophenyl)aminium hexachloroantimonate to give cationic [L_OEtRuCl₂(NPCy₃)][SbCl₆]. Chlorination of [L_OEtRuCl]₂(μ-Cl)₂ with PhICl₂ yielded the Ru(IV) complex L_OEtRuCl₃. Refluxing [L_OEtRuCl]₂(μ-Cl)₂ with 1-azidoadamantane in toluene afforded the Ru(IV) metallacyclic L_OEtRuCl[κ₂-N,C-(AdNCHC₆H₄)], possibly via double C-H activation of toluene by a Ru(IV) adamantylimido intermediate. Treatment of [L_OEtRuCl]₂(μ-Cl)₂ with p-nitrophenyl azide gave the Ru(III) amine complex L_OEtRuCl₂(NH₂C₆H₄NO₂-4).

Treatment of [Ir(COE)₂]₂(μ-Cl)₂ (COE = cis-cyclooctene) with AgL_OEt resulted in the formation of L_OEtIrCl₂(COE) that reacted with AgNO₃, dtbpy and NH₄PF₆ to afford [L_OEtIr(dtbpy)(COE)][PF₆]₂. Oxidation of L_OEtIrCl₂(COE) with ozone in CH₂Cl₂ led to formation of the Ir(IV) complex L_OEtIrCl₃. Alternatively, reaction of L_OEtIrCl₂(COE) with PhICl₂ also gave L_OEtIrCl₃ that exhibited the Ir(IV/III) potential at ca. 0 V vs. Cp₂Fe^+/0. Reaction of [Rh(COE)₂]₂(μ-Cl)₂ with AgL_OEt gave [L_OEtRhCl]₂(μ-Cl)₂. Heating [L_OEtRhCl]₂(μ-Cl)₂ with excess t-BuNH₂ in THF afforded L_OEtRhCl(NH₂-t-Bu)₂Cl. Treatment of Rh(N^N)Cl₃(DMF) (DMF = N,N-dimethylformamide), AgL_OEt and AgOTf in acetone gave [L_OEtRh(N^N)Cl]OTf (N^N = dtbpy and bpy). Reaction of [L_OEtRh(bpy)Cl]OTf with AgOTf in acetone resulted the formation of water-soluble [L_OEtRh(bpy)(acetone)][OTf]₂.

Reaction of (L_OEt)₂Zr(NO₃)₂ with KMnO₄ gave (L_OEt)₂Zr(MnO₄)₂. Reaction of (L_OEt)₂Ce(NO₃)₂ with K₂[Os(O)₂(OH)₄] afforded a grey precipitate which was slowly converted to the dinuclear Ce(IV) oxalate complex [(L_OEt)₂Ce]₂(μ-C₂O₄) upon recrystallization from methanol in air.

(L_OEt)₂Ce(MnO₄)₂ can oxidize alkylbenzenes such as toluene, ethylbenzene, and cumene to give the corresponding alcohol and/or aldehyde/ketone products. By contrast, (L_OEt)₂Zr(MnO₄)₂ is incapable of alkylbenzene oxidation. The kinetics of stoichiometric oxidation of ethylbenzene with (L_OEt)₂Ce(MnO₄)₂ has been studied. At room temperature, the oxidation of neat ethylbenzene with (L_OEt)₂Ce(MnO₄)₂ was found to follow pseudo-first-order kinetics with an observed rate constat of k_obs = (3.3 ± 0.3) × 10^-4 s^-1. The kinetic isotope effect (k_H/k_D) for the oxidation of ethylbenzene was determined to be 6.0 ± 0.5, suggesting that a hydrogen atom transfer mechanism is involved in the C-H oxidation. (L_OEt)₂Ce(MnO₄)₂ is capable of catalyzing aerobic oxidation of ethylbenzene at room temperature with a turnover number (TON) of about 9. Ce(III) and -(IV) L_OEt complexes were found to be active catalysts for aerobic oxidation of cumene at 100 ℃. For example, aerobic oxidation of neat cumene in the presence of a catalytic amount of [(L_OEt)₂Ce(H₂O)₂]Cl (1.0 mM) at 100 ℃ resulted in the formation of a mixture of cumyl alcohol, cumyl hydroperoxide and acetophenone with a total conversion of 95% and total turnover of 6810 in 20 h. It is believed that the L_OEtCe-catalyzed aerobic oxidation of cumene at high temperature proceeds via a free radical mechanism.