103533-54-6Relevant academic research and scientific papers
Production of Formamides from CO and Amines Induced by Porphyrin Rhodium(II) Metalloradical
Zhang, Jiajing,Zhang, Wentao,Xu, Minghui,Zhang, Yang,Fu, Xuefeng,Fang, Huayi
supporting information, p. 6656 - 6660 (2018/05/24)
It is of fundamental importance to transform carbon monoxide (CO) to petrochemical feedstocks and fine chemicals. Many strategies built on the activation of C≡O bond by π-back bonding from the transition metal center were developed during the past decades. Herein, a new CO activation method, in which the CO was converted to the active acyl-like metalloradical, [(por)Rh(CO)]? (por = porphyrin), was reported. The reactivity of [(por)Rh(CO)]? and other rhodium porphyrin compounds, such as (por)RhCHO and (por)RhC(O)NHnPr, and corresponding mechanism studies were conducted experimentally and computationally and inspired the design of a new conversion system featuring 100% atom economy that promotes carbonylation of amines to formamides using porphyrin rhodium(II) metalloradical. Following this radical based pathway, the carbonylations of a series of primary and secondary aliphatic amines were examined, and turnover numbers up to 224 were obtained.
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).
