NICASIO JARAMILLO , María Del Carmen

Microkinetic modeling is a computational tool that allows simulating the evolution of the concentration of catalytically relevant species with time, providing a description of the catalytic system closer to the experimental. Microkinetic models have been mainly applied in organometallic catalysis as a means for validating mechanistic proposals...

Aryl-Pd(ii) chlorides stabilized by dialkylterphenyl phosphine ligands undergo a thermal isomerization process, leading to the formation of allyl-Pd(ii)-chloride species. The transformation involves the intramolecular functionalization of a C-H bond of the terphenyl group mediated by the Pd(ii) center.

A series of 2-aminobiphenyl palladacycles supported by dialkylterphenyl phosphines, PR2Ar′ (R=Me, Et, iPr, Cyp (cyclopentyl), Ar′=ArDipp2, ArXyl2f, Dipp (2,6-C6H3-(2,6-C6H3-(CHMe2)2)2), Xyl=xylyl) have been prepared and structurally characterized. Neutral palladacycles were obtained with less bulky terphenyl phosphines (i.e., Me and Et...

Among phenol-derived electrophiles, aryl sulfamates are attractive substrates since they can be employed as directing groups for C–H functionalization prior to catalysis. However, their use in C–N coupling is limited only to Ni catalysis. Here, we describe a Pd-based catalyst with a broad scope for the amination of aryl sulfamates. We show that...

Electron deficient azides are challenging substrates in CuAAC reactions. Particularly, when N-carbonyl azides are applied the formation of N-carbonyl triazoles has not yet been observed. We report herein the first example of this class of reaction, with a copper-based system that efficiently enables the synthesis of N-carbamoyl 1,2,3-triazoles...

The reaction of 1-alkynes with acyl azides in the presence of [Tpm *,BrCu(NCMe)]BF4 [Tpm*,Br = tris(3,5-dimethyl-4-bromopyrazolyl)methane] as the catalyst provides 2,5-oxazoles in moderate to high yields. This is a novel transformation of the CuAAC type that constitutes a significant variation of the commonly observed [3 + 2] cycloaddition...

Despite the excellent catalytic properties display by NHC-Pd-PEPPSI complexes in cross-coupling, phosphane analogs have been barely screened. In this work, we report the synthesis and characterization of a series of LPdCl2(amine) complexes bearing dialkylterphenyl phosphanes (PR2Ar′) and pyridine or morpholine ligands. The novel compounds have...

Ni-catalyzed C−S cross-coupling reactions have received less attention compared with other C-heteroatom couplings. Most reported examples comprise the thioetherification of most reactive aryl iodides with aromatic thiols. The use of C−O electrophiles in this context is almost uncharted. Here, we describe that preformed Ni(II) precatalysts of...

A series of Au(I)/Pt(0) combinations that behave as bimetallic frustrated Lewis pairs activates dihydrogen in a cooperative manner. The steric bulk of the terphenyl phosphines that stabilize both fragments allows for the isolation of a rather unique and highly distorted cis-type dihydride platinum(II) structure.

Bulky terphenyl phosphane ligands PMe2Ar′ (Ar′ = terphenyl group) facilitate the isolation of zero-valent bis-phosphane complexes of nickel, palladium and platinum. The former show coordination numbers greater than two in the solid state due to the existence of Ni-Careneinteractions with the terphenyl fragment.

Neutral and cationic N-methyl- and N-phenyl-2-aminobiphenyl methanesulfonate palladacycles stabilized with dialkylterphenyl phosphanes have been prepared and characterized. Neutral structures are favored with the less bulky phosphane PMe2ArXyl2, L1, while more sterically demanding ligands PiPr2ArXyl2, L3, and PCyp2ArXyl2 (Cyp = cyclopentyl),...

Several dinuclear terphenyl phosphine copper(I) halide complexes of composition [CuX(PR2Ar′)]2 (X = Cl, Br, I; R = hydrocarbyl, Ar′ = 2,6-diarylterphenyl radical), 1-5, have been isolated from the reaction of CuX with 1 equiv of the phosphine ligand. Most of them have been characterized by X-ray diffraction studies in the solid state, thus...

The experimental and computational characterization of a series of dialkylterphenyl phosphines, PR2Ar′ is described. The new P‐donors comprise five compounds of general formula PR2Arurn:x-wiley:09476539:media:chem201803598:chem201803598-math-0001 (R=Me, Et, iPr, c‐C5H9 and c‐C6H11);...

The stereoelectronic properties of a series of sterically hindered phosphines containing a terphenyl substituent, PR2Ar' (R = alkyl; Ar' = C6H3-2,6-Ar2), have been evaluated by various methods. Their σ-donating capacity has been assessed on the basis of the carbon monoxide stretching frequencies in benchmark iridium [IrCl(CO)2(PR2Ar')] and...

A series of enantiopure chiral NH2/SO palladium complexes have been synthesised with high yields by treating the corresponding tert-butylsulfinamide/sulfoxide derivatives with Pd(CH3CN)2Cl2. The enantiopure chiral ligands were prepared by stereoselective addition of tert-butyl or phenyl methylsulfinyl carbanions to different...