13471-37-9Relevant academic research and scientific papers
Addition of E-H (E = N, P, C, O, S) Bonds to Heterocumulenes Catalyzed by Benzimidazolin-2-iminato Actinide Complexes
Liu, Heng,Fridman, Natalia,Tamm, Matthias,Eisen, Moris S.
supporting information, p. 3896 - 3903 (2017/10/30)
The synthesis and characterization of benzimidazolin-2-iminato actinide(IV) complexes [(BimR1/R2N)An(N{SiMe3}2)3] (An = U, Th) (1-6) is reported. All complexes were obtained in high yields, and their solid state structures were established through single-crystal X-ray diffraction analysis. Using 1-6 as precatalysts, the addition of mono- and bifunctional E-H (E = N, P, C, O, S) substrates to various heterocumulenes, including carbodiimides, isocyanates, and isothiocyanates, was investigated, affording the respective addition products in high yields under very mild reaction conditions. Various amines were applicable to this reaction, indicating a large scope capability of amine nucleophiles for the insertion process.
Copper-catalyzed oxidative three-component synthesis of N, N′, N′-trisubstituted guanidines
Li, Jihui,Neuville, Luc
, p. 6124 - 6127 (2014/01/17)
A copper-catalyzed three-component synthesis of trisubstituted N-aryl guanidines involving cyanamides, arylboronic acids, and amines has been developed. This operationally simple oxidative process, which is performed in the presence of K2CO3, a catalytic amount of CuCl 2·2H2O, bipyridine, and oxygen (1 atm), allows the rapid assembly of N,N′,N″-trisubstituted aryl guanidines.
Guanidinato complexes of iridium: Ligand-donor strength, O2 reactivity, and (alkene)peroxoiridium(III) intermediates
Kelley, Matthew R.,Rohde, Jan-Uwe
, p. 2564 - 2580 (2013/04/10)
A series of seven [Ir{ArNC(NR2)NAr}(cod)] complexes (1a-1g; where R = Me or Et; Ar = Ph, 4-MeC6H4, 4-MeOC 6H4, 2,6-Me2C6H3, or 2,6-iPr2C6H3; and cod = 1,5-cyclooctadiene) were synthesized by two different methods from the neutral guanidines, ArN-C(NR2)NHAr, using either MeLi and [{Ir(cod)} 2(μ-Cl)2] or [{Ir(cod)}2(μ-OMe) 2]. Reaction of 1a-1g with CO produced the corresponding [Ir{ArNC(NR2)NAr}(CO)2] complexes (2a-2g), which were characterized by NMR and solution- and solid-state IR spectroscopy. Complexes 1b (R = Et, Ar = Ph), 1d (R = Et, Ar = 4-MeC6H4), 1f (R = Me, Ar = 2,6-Me2C6H3), and 2b (R = Et, Ar = Ph) were characterized by X-ray crystallography as mononuclear complexes with a guanidinato-κ2N,N′ ligand and a cod or two CO ligands coordinated to the Ir center in a distorted square-planar environment. On the basis of the CO stretching frequencies of 2a-2g [avg. νCO (n-pentane) = 2016-2019 cm-1] and the alkene 13C chemical shifts of 1a-1g [δ(13CC-C) = 58.7-61.0 ppm], the donor strength of the guanidinato ligands was evaluated and compared to that of related monoanionic ligands. Reaction of 1a-1g in solution with O2 at 20 C afforded (alkene)peroxoiridium(III) intermediates, [Ir{ArNC(NR 2)NAr}(cod)(O2)] (3). The steric properties of the supporting ligand play a decisive role in O2 binding in that complexes without ortho substituents react largely irreversibly with O 2 (1a-1e; where Ar = Ph, 4-MeC6H4 or 4-MeOC6H4), whereas complexes with ortho substituents exhibit fully reversible O2 binding (1f and 1g; where Ar = 2,6-Me2C6H3 or 2,6-iPr 2C6H3). Complexes 3a-3f were characterized by 1H NMR and IR spectroscopy (νOO = 857-872 cm -1). Decay of the new intermediates and subsequent reaction with cod produced 4-cycloocten-1-one and the respective IrI precursor.
