18843-79-3Relevant academic research and scientific papers
Hydrophosphination of CO2 and Subsequent Formate Transfer in the 1,3,2-Diazaphospholene-Catalyzed N-Formylation of Amines
Chong, Che Chang,Kinjo, Rei
supporting information, p. 12116 - 12120 (2015/10/12)
Hydrophosphination of CO2 with 1,3,2-Diazaphospholene (NHP-H; 1) afforded phosphorus formate (NHP-OCOH; 2) through the formation of a bond between the electrophilic phosphorus atom in 1 and the oxygen atom from CO2, along with hydride transfer to the carbon atom of CO2. Transfer of the formate from 2 to Ph2SiH2 produced Ph2Si(OCHO)2 (3) in a reaction that could be carried out in a catalytic manner by using 5 mol % of 1. These elementary reactions were applied to the metal-free catalytic N-formylation of amine derivatives with CO2 in one pot under ambient conditions.
Matrix isolation infrared and density functional theoretical studies of organic silanones, (CH3O)2Si=O and (C6H5)2Si=O
Khabashesku, Valery N.,Kerzina, Zoya A.,Kudin, Konstantin N.,Nefedov, Oleg M.
, p. 45 - 59 (2007/10/03)
Transient organic silanones (CH3O)2Si=O (3) and (C6H5)2Si=O (4) were generated by vacuum pyrolysis from 3,3-dimethoxy-6-oxa-3-silabicyclo[3.1.0]hexane (6) and its 3,3-diphenyl derivative (7), respectively, and after being trapped in argon cryogenic matrices at 12 K directly studied by IR spectroscopy. Vibrational assignments in the observed IR spectra of 3 and 4 have been made by comparison with the density functional theory B3LYP/6-311G(d, p) calculated harmonic frequencies and infrared intensities for these molecules and for the other silanones, H2Si=O (1), (CH3)2Si=O (2), and CH3(CH3O)Si=O (5), studied earlier by matrix isolation techniques. The observed bands at 1247 cm-1 in 3 and at 1205 cm-1 in 4 were assigned to the Si=O stretching modes, which under the influence of the same substituents show the similar frequency shifts as ν (M=O) in ketones, phosphinoxides, and sulfoxides. Under the conditions of vacuum pyrolysis studied the diphenylsilanone 4 was found to be more thermodynamically stable than the dimethoxy derivative 3, while the latter indicated a higher kinetic stability towards cyclooligomerization than the silanones 2 and 4.
