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Relevant academic research and scientific papers

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.

Highly Active Dinuclear Titanium(IV) Complexes for the Catalytic Formation of a Carbon-Heteroatom Bond

A series of mononuclear titanium(IV) complexes with the general composition κ3-[R{NHPh2P(X)}2Ti(NMe2)2] [R = C6H4, X = Se (3b); R = trans-C6H10, X = S (4a), Se (4b)] and [{κ2-N(PPh2Se)2}2Ti(NMe2)2] (6b) and two dinuclear titanium(IV) complexes, [C6H4{(NPh2PS)(N)}Ti(NMe2)]2 (3c) and [{κ2-N(PPh2Se)}Ti(NMe2)2]2 (6c), are reported. Dinuclear titanium(IV) complex 6c acts as an efficient catalyst for the chemoselective addition of an E-H bond (E = N, O, S, P, C) to heterocumulenes under mild conditions. The catalytic addition of aliphatic and aromatic amines, alcohol, thiol, phosphine oxide, and acetylene to the carbodiimides afforded the corresponding hydroelemented products in high yield at mild conditions with a broader substrate scope. The catalytic efficiency of the dinuclear complex depends on the cooperative effect of the TiIV ions, the systematic variation of the intermetallic distance, and the ligand's steric properties of the complex, which enhances the reaction rate. Most interestingly, this is the first example of catalytic insertion of various E-H bonds into the carbodiimides using a single-site catalyst because only the titanium-mediated insertion of E-H into a C-N unsaturated bond is reported to date. The amine and alcohol insertion reaction with the carbodiimides showed first-order kinetics with respect to the titanium(IV) catalyst as well as substrates. A most plausible mechanism for hydroelementation reaction is also proposed, based on the spectroscopic data of the controlled reaction, a time-course study, and the Hammett plot.

Rare-earth metal tris(trimethylsilylmethyl) anionic complexes bearing one 1-phenyl-2,3,4,5-tetrapropylcyclopentadienyl ligand: Synthesis, structural characterization, and application

Synthesis and structural characterization of half-sandwich rare-earth metal tris(trimethylsilylmethyl) anionic complexes bearing one 1-phenyl-2,3,4,5- tetrapropylcyclopentadienyl ligand are achieved. These soluble anionic compounds show good reactivity in