103533-60-4Relevant academic research and scientific papers
Mild and selective C(CO)-C(α) bond activation of ketones with rhodium(III) porphyrin β-hydroxyethyl
Chan, Chung Sum,Lee, Siu Yin,Chan, Kin Shing
, p. 151 - 156 (2013/02/25)
Rhodium(III) porphyrin β-hydroxyethyl, RhIII(ttp)CH 2CH2OH (ttp = 5,10,15,20-tetratolylporphyrinato dianion), was found to serve as a precursor of the highly reactive RhIII(ttp)OH for the C(CO)-C(α) bond activation (CCA) of ketones under mild and aerobic conditions of 25-50 C.
Mild and selective c(co)c(α) bond cleavage of ketones by rhodium(iii) porphyrins: Scope and mechanism
Fung, Hong Sang,Li, Bao Zhu,Chan, Kin Shing
experimental part, p. 570 - 579 (2012/04/10)
Rhodium(III) porphyrins were found to undergo selective C(CO)C(α) bond activation (CCA) of ketones promoted by water at temperatures as low as 50 °C. The acyl group of the ketone was transferred to the rhodium center, and the alkyl fragment was oxidized to a carbonyl moiety accordingly. The hydroxyl group of water is transferred to the rhodium porphyrin through hydrolysis of the kinetic α- carbonhydrogen bond activation (α-CHA) product to give RhIII(ttp)OH (ttp = 5,10,15,20-tetratolylporphyrinato dianion), which subsequently cleaves the C(CO)C(α) bond of ketone.
Sterically enhanced, selective C(CO)-C(α) bond cleavage of a ketones by rhodium porphyrin methyl
Fung, Hong Sang,Li, Bao Zhu,Chan, Kin Shing
, p. 4421 - 4423 (2011/01/07)
Selective carbon(CO)-carbon(α) bond activation of ketones was achieved by rhodium(III) 5,10,15,20-tetrakis-4-toylporphyrinato methyl (Rh(ttp)Me (1)) to yield the corresponding rhodium porphyrin acyls at temperatures as low as 50 °C. More hindered isopropyl ketones were much more reactive than ethyl or methyl ketones. Rh(ttp)OH (3a) was proposed to be the intermediate to cleave the C(CO)-C(α) bond.
Organometallic chemistry of rhodium tetraphenylporphyrin derivatives: Formyl, hydroxymethyl, and alkyl complexes
Wayland, Bradford B.,Van Voorhees, Seth L.,Wilker, Charles
, p. 4039 - 4042 (2008/10/08)
Organometallic reactivity patterns of the rhodium tetraphenylporphyrin derivatives Rh(TPP)(H), Rh(TPP)-, and (Rh(TPP))2 are found to closely parallel those of the corresponding rhodium octaethylporphyrin species. Preparation and physical properties of the formyl, hydroxymethyl, and alkyl complexes of Rh(TPP) are described along with the photoinduced insertion of carbon monoxide into the Rh-CH3 bond. Thermodynamic values for the reaction Rh(TPP)(H) + CO ? Rh(TPP)(CHO) in C6D6 are ΔH° = -42 kJ/mol and ΔS° = -89 ± 15 J/(K mol).
