18406-59-2Relevant articles and documents
Luminescent Ce(III) Complexes as Stoichiometric and Catalytic Photoreductants for Halogen Atom Abstraction Reactions
Yin, Haolin,Carroll, Patrick J.,Anna, Jessica M.,Schelter, Eric J.
, p. 9234 - 9237 (2015)
Luminescent Ce(III) complexes, Ce[N(SiMe3)2]3 (1) and [(Me3Si)2NC(RN)2]Ce[N(SiMe3)2]2 (R = iPr, 1-iPr; R = Cy, 1-Cy), with C3v and C2v solution symmetries display absorptive 4f → 5d electronic transitions in the visible region. Emission bands are observed at 553, 518, and 523 nm for 1, 1-iPr, and 1-Cy with lifetimes of 24, 67, and 61 ns, respectively. Time-dependent density functional theory (TD-DFT) studies on 1 and 1-iPr revealed the 2A1 excited states corresponded to singly occupied 5dz2 orbitals. The strongly reducing metalloradical character of 1, 1-iPr, and 1-Cy in their 2A1 excited states afforded photochemical halogen atom abstraction reactions from sp3 and sp2 C-X (X = Cl, Br, I) bonds for the first time with a lanthanide cation. The dehalogenation reactions could be turned over with catalytic amounts of photosensitizers by coupling salt metathesis and reduction to the photopromoted atom abstraction reactions.
Preliminary communication. Primary aminomethylation of organometallic compounds via N,N-bis(trimethylsilyl)methylthiomethylamine
Fiocca, Luisa,Fiorenza, Mariella,Reginato, Gianna,Ricci, Alfredo,Dembech, Pasquale,Seconi, Giancarlo
, p. C23 - C26 (1988)
The reaction of various organometallic compounds with N,N-bis(trimethylsilyl)methylthiomethylamine provides an easy way for the introduction of primary aminomethyl unit into a variety of organic substrates.
Quantitative Silylation Speciations of Primary Phenylalkyl Amines, Including Amphetamine and 3,4-Methylenedioxyamphetamine Prior to Their Analysis by GC/MS
Molnár, Borbála,Fodor, Blanka,Boldizsár, Imre,Molnár-Perl, Ibolya
, p. 10188 - 10192 (2015/11/09)
A novel, quantitative trimethylsilylation approach derivatizing 11 primary phenylalkyl amines (PPAAs), including amphetamine (A) and 3,4-methylenedioxyamphetamine (MDA), was noted. Triggering the fully derivatized ditrimethylsilyl (diTMS) species with the N-methyl-N-(trimethylsilyl)-trifluoroacetamide (MSTFA) reagent, a new principle was recognized followed by GC/MS. In the course of method optimization, the complementary impact of solvents (acetonitrile, ACN; ethyl acetate, ETAC; pyridine, PYR) and catalysts (trimethylchlorosilane, TMCS; trimethyliodosilane, TMIS) was studied: the role of solvent and catalyst proved to be equally crucial. Optimum, proportional, huge responses were obtained with the MSTFA/PYR = 2/1-9/1 (v/v) reagent applying catalysts; A and MDA needed the TMIS, while the rest of PPAAs provided the diTMS products also with TMCS. Similar to derivatives generated with hexamethyldisilazane and perfluorocarboxylic acid (HMDS and PFCA) (Molnár et al. Anal. Chem. 2015, 87, 848'852), the fully silylated PPAAs offer several advantages. Both of our methods save time and cost by allowing for direct injection of analytes into the column; this is in stark contrast with the requirement to evaporate acid anhydrides by nitrogen prior to their injection. Efficiences of the novel catalyzed trimethylsilylation (MSTFA) and our recently introduced (now, for A and MDA extended) acylation principle were contrasted. Catalyzed trimethylsilylation led to diTMS derivatives resulting in on average a 1.7 times larger response compared to the corresponding acylated species. Catalyzed trimethylsilylation of PPAAs, A, and MDA were characterized with retention, mass fragmentation, and analytical performance properties (R2, LOQ values). The practical utility of ditrimethylsilyation was shown by analyzing A in urine and mescaline (MSC) in cactus samples.
