Carbonyl-stabilized phosphorus ylides R3PCHC(O)R‘ (R = Ph, Tol-p; R‘ = OEt, OMe,
NMe2) react with the 1,5-cyclooctadiene complexes [MCl2(cod)] (M = Pt, Pd; cod = C8H12 =
1,5-cyclooctadiene) to give the monomeric cyclooctenyl complexes [MCl2{C8H12{CH(PR3)C(O)R‘}}]. The ylides attack in an exo fashion to give complexes which can be regarded as
metalated phosphonium salts. Reactions involving the replacement of one or both chloro
ligands with a neutral ligand are discussed. The crystal structures of complexes [PtCl2{C8H12{CH(PPh3)CO2Me}}] and [Pt{C8H12{CH(PPh3)CO2Me}}(py)2](CF3SO3)2 are reported.
Empty fruit bunch (EFB) of oil palm trees was converted to fermentable sugars by the combined use of dilute acids and whole fungal cell culture-catalyzed hydrolyses. EFB (5%, w/v) was hydrolyzed in the presence of 0.5% H2 SO4 and 0.2% H3 PO4 at 160 °C for 10 Min. The solid fraction was separated from the acid hydrolysate by filtration and subjected to enzymatic hydrolysis at 50 °C using the whole cell culture of Trichoderma reesei RUT-C30 (2%, w/v), which was prepared by cultivation at 30 °C for 7 days to reach its maximal cellulase activity. The combined hydrolyses of EFB gave a total sugar yield of 82.0%. When used as carbon sources for cultivating Escherichia coli in M9 medium at 37 °C, the combined EFB hydrolysates were shown to be more favorable or at least as good as pure glucose for cell growth in terms of the higher (1.1 times) optical density of E. coli cells. The by-products generated during the acid-catalyzed hydrolysis did not seem to obviously affect cell growth. The combined use of acid and whole cell culture hydrolyses might be a commercially promising method for pretreatment of lignocellulose to get fermentable sugars.
The carbonyl-stabilized phosphorus ylides Ph3PCHCO2R (R = Me, Et) react with the
platinum complexes [PtCl(η2-CH2CH2)(N,N,N‘,N‘-tetramethylethylenediamine)]ClO4 and
[PtCl2(η4-diene)] (diene = 1,5-hexadiene (C6H10), dicyclopentadiene (C10H12), 4-vinylcyclohex-1-ene (C8H12), norbornadiene (C7H8)) to give complexes resulting from nucleophilic attack of
the ylide at one of the olefinic carbons. The crystal structures of [PtCl2{η3-C6H10CH(PPh3)CO2Et}], [PtCl2{η3-C10H12CH(PPh3)CO2Me}]·0.5CH2Cl2, and [PtCl2{η3-C8H12CH(PPh3)CO2Me}]·2CHCl3 are reported and indicate an exo attack in the case of the dicyclopentadiene complex
and anti-Markovnikov addition (attack at the CH2 group) in the other two complexes.
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