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Relevant academic research and scientific papers

Synthesis and characterization of bridged bis(amidato) rare earth metal amides and their applications in C-N bond formation reactions

Based on three bisamide proligands H2Ln (n = 1-3) (H2L1 = [(Me3C6H2CONHCH2)2CH2], H2L2 = [(Me3C6H2CONHCH2)2C(CH3)2], H2L3 = [Me3C6H2CONH(CH2)2]2NCH3), eight bis(amidato) trivalent rare-earth metal amides {LnRE[N(TMS)2]}2 (n = 1, RE = La (1), Sm (2), Nd (3), Y (4); n = 2, RE = La (5), Nd (6); n = 3, RE = La (7), Nd (8); TMS = SiMe3) were successfully synthesized by treatment of H2Ln with RE[N(TMS)2]3 in a 1:1 molar ratio. Complexes 3, and 5-8 were characterized by single-crystal X-ray diffraction, and NMR characterization was carried out for the La complexes 1, 5, 7 and the Y complex 4. These complexes exhibited high catalytic activities in both the direct amidation of aldehydes and the addition of amines with carbodiimine. It was found that the bis(amidato) rare earth metal amides bearing different linkers have different effects on the transformations and lanthanum and neodymium complexes performed better than others.

An amidato divalent ytterbium cluster: Synthesis and molecular structure, its reactivity to carbodiimides and application in the guanylation reaction

A divalent ytterbium amidate 1 ([Yb3L6]·2C7H8 for short) was synthesized via amine-elimination of Yb[N(SiMe3)2]2(TMEDA) with an amide proligand N-2,6-diisopropylphenylbenzamide HL (L = 2,6-iPr2C6H3NC(O)Ph) and structurally characterized to be a trinuclear symmetric cluster. Further studies on the reduction of iPrNCNiPr by complex 1 provide Yb(iii) complex 2 in hexane-THF ([(YbL2)2(μ-NiPrCNiPr)][YbL3(THF)]·C7H8), which is composed of two subunits in a unit cell, one is a bridged Yb(iii) carbene, just the same as complex 4 ([(YbL2)2(μ-NiPrCNiPr)]·3C7H8) obtained in the same reaction in toluene, and the other is a homoleptic monomeric Yb(iii) amidate (YbL3). It is also found that complex 2 decomposed to complex 3 ([YbL3]2·2C7H8) and 4 at 90 °C in toluene. Complexes 1-4 were confirmed by X-ray structure determination. Furthermore, complex 4 was proved to be a more active species than its precursor 1 in the catalytic addition of amines to carbodiimides. Finally, complex 1 was found to be an excellent pre-catalyst for the guanylation reaction with a wide scope of substrates.

Combination of air/moisture/ambient temperature compatible organolithium chemistry with sustainable solvents: Selective and efficient synthesis of guanidines and amidines

Highly-efficient and selective fast addition of in situ generated lithium amides [LiN(H)R] (obtained via an acid-base reaction between n-BuLi and the desired primary amine) into carbodiimides (R-NCN-R) or nitriles (R-CN) has been studied, for the first ti

Catalytic Carbodiimide Guanylation by a Nucleophilic, High Spin Iron(II) Imido Complex

Reduction of the three-coordinate iron(III) imido [Ph2B(tBuIm)2FeNDipp] (1) affords [Ph2B(tBuIm)2FeNDipp][K(18-C-6)THF2] (2), a rare example of a high-spin (S = 2) iron(II) imido complex. Unusually for a late metal imido complex, the imido ligand in 2 has

Cyclic (Alkyl)amino Carbene Complex of Aluminum(III) in Catalytic Guanylation Reaction of Carbodiimides

Herein we report the synthesis of a cyclic (alkyl)amino carbene (cAAC) complex of AlMe3. This complex was used as an efficient catalyst for the guanylation reaction of carbodiimides with primary arylamines and secondary amines to deliver guanidine derivatives in good to excellent yields. This catalytic protocol can tolerate a wide range of functional groups. Furthermore, the longevity of the catalyst was tested in successive catalytic cycles, which indicated a sustained catalytic activity over a multiple cycles. The mechanistic pathway was well understood with the help of stoichiometric reaction and DFT study.

Addition of E-H (E = N, P, C, O, S) Bonds to Heterocumulenes Catalyzed by Benzimidazolin-2-iminato Actinide Complexes

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.

Ph3P/I2-mediated synthesis of N,N′,N″-substituted guanidines and 2-iminoimidazolin-4-ones from aryl isothiocyanates

A convenient one-pot procedure for the synthesis of acyclic and cyclic guanidines mediated by the Ph3P/I2 system is described. Sequential condensation of aryl isothiocyanates with amines followed by dehydrosulfurization and guanylation could lead to both symmetric and unsymmetric N,N′,N″-substituted derivatives. Through a tandem guanylation-cyclization, a series of 2-iminoimidazolin-4-ones could also be prepared in good yields from the reaction of aryl isothiocyanates with amino acid methyl esters.

One-Pot Synthesis of C2 Symmetric and Asymmetric N,N′,N″-Substituted Guanidines from Aryl Isothiocyanates and Amines

Highly substituted guanidines were conveniently prepared through a one-pot reaction between aryl isothiocyanates and amines mediated by the Ph3P-I2/Et3N system. The C 2-symmetric N,N′,N″-substituted guanidines were readily accessed using a 1:2 molar ratio of an aryl isothiocyanate and an amine; while sequential addition of two different amines in equimolar ratios gave rise to asymmetric derivatives. Both primary and secondary amines were found to react preferentially with electron-deficient aryl isothiocyanates, rapidly providing guanidines in good yields under mild conditions.

Phenylene-bridged β-Ketoiminate Dilanthanide Aryloxides: Synthesis, Structure, and Catalytic Activity for Addition of Amines to Carbodiimides

The synthesis and reactivity of a series of bimetallic lanthanide aryloxides stabilized by a p-phenylene-bridged bis(β-ketoiminate) ligand is presented. The reaction of 1,4-diaminobenzene with acetylacetone in a 1:2.5 molar ratio in absolute ethanol gave

Catalytic addition of amines to carbodIImides by bis(β-diketiminate)lanthanide(II) complexes and mechanistic studies

Reduction reactions of bis(β-diketiminate)lanthanide(iii) chlorides formed in situ by reactions of anhydrous LnCl3 with 2 equiv. of sodium salt of the β-diketiminate ligand in THF with a Na/K alloy afforded a series of bis(β-diketiminate)lanthanide(ii) complexes LnL2(THF)n (L = L26-Me2 = [N(2,6-Me2C6H3)C(Me)]2CH-, n = 1, Ln = Eu (1); L = L2,4,6-Me3 = [N(2,4,6-Me3C6H2)C(Me)]2CH-, n = 1, Ln = Eu (2); L = L2,6-iPr2 = [N(2,6-iPr2C6H3)C(Me)]2CH-, n = 0, Ln = Eu (3), Sm (4); L = L2,6-ipr2Ph = [(2,6-iPr2C6H3)NC(Me)CHC(Me)N(C6H5)]-, n = 0, Ln = Eu (5), Yb (6); L = L2-Me = [N(2-MeC6H4)C(Me)]2CH-, n = 1, Ln = Yb (7)) in high yields. All the complexes, especially the complexes of SmII (4) and EuII (5), were found to be excellent pre-catalysts for catalytic addition of amines to carbodiimides to multi-substituted guanidines with a wide scope of substrates. The activity depends both on the central metals and the ligands with the active sequence of YbII II and EuII II and L2,6-Me2 2,4,6-Me3 ～ L2,6-iPr2 2,6-ipr2Ph for the ligands. The mechanistic study by the isolation of guanidinate species and their reactivity revealed that EuII monoguanidinate complexes Eu(L2,6-Me2)[(C6H5N)C(NHCy)(NCy)](DME) (8) and Eu(L2,6-ipr2Ph)[(C6H5N)C(NHCy)(NCy)](THF)2 (9) should be the key active intermediates for the systems with EuII complexes and a YbIII bis(guanidinate) complex Yb(L2-Me)[(C6H5N)C(NHCy)(NCy)]2 (11) for the system using a YbII complex.