10.1021/ic050985r
This study investigates the synthesis, structures, and reactivity of new pentamethylcyclopentadienyl-rhodium(III) and -iridium(III) 4-acyl-5-pyrazolonate complexes. The researchers synthesized various complexes by reacting [{(η5-Cp*)MCl}2(μ-Cl)2] (where M = Rh or Ir) with sodium salts of acylpyrazolones (NaQ), specifically 1-phenyl-3-methyl-4R(CdO)-pyrazol-5-ones, to produce [Cp*M(Q)Cl] derivatives. The study utilized chemicals such as toluene, dichloromethane, and various sodium salts of acylpyrazolones (HQ) to facilitate the formation of these complexes. The purpose of using these chemicals was to explore the coordination chemistry of rhodium and iridium with the acylpyrazolonate ligands, which are known for their stability and potential applications in catalysis, while also examining their structural and reactivity properties through various analytical techniques.
10.1002/anie.201000160
The researchers identified N-alkoxy-N-alkyl amides as effective tethers for C-H insertion reactions, leading to amino-hydroxy functionalized systems. They demonstrated, through computational and experimental methods, that the C-H insertion site selectivity can be modulated by reaction conditions and the electronics of the ligand of the dirhodium catalyst. The study concluded that the N-O tether is a versatile and atom-economical tether that facilitates remote C-H functionalization, and its value lies in its ability to be transformed into several different functionalities, which can be further elaborated into diverse moieties. Key chemicals used in the process include N-alkoxy-N-alkyl diazoamides, dirhodium catalysts, and various rhodium and ruthenium complexes to influence the product distribution.
10.1016/S0022-328X(01)00720-3
The research aimed to explore the reactivity of rhodium hydride complexes with aryldiazonium cations, focusing on the synthesis and characterization of aryldiazene complexes of rhodium. The study was motivated by the interest in transition metal complexes containing partially reduced dinitrogen ligands, such as aryldiazenido and aryldiazene, due to their potential relevance in nitrogen fixation and their unique coordination modes and properties. The researchers synthesized aryldiazene complexes [Rh(ArNNH)(CO)(PPh3)3]BF4 (1) and [Rh(ArNNH)(PPh3)4]BF4 (2) using hydride species RhH(CO)(PPh3)3 and RhH(PPh3)4, which reacted with aryldiazonium cations at low temperatures. The complexes were characterized using IR and 1H-, 31P-, and 15N-NMR spectra. The study concluded that the synthesized aryldiazene complexes were thermally unstable and did not lead to arylhydrazine derivatives upon reaction with H2, contrasting with previous studies that suggested such reductions were possible. Key chemicals used in the process included aryldiazonium cations, RhH(CO)(PPh3)3, RhH(PPh3)4, and solvents like CH2Cl2 and EtOH for the reactions and characterizations.
10.1021/ja061430d
The research study on the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to 3-substituted maleimides, aiming to construct quaternary carbon stereocenters with high regio- and enantioselectivity. The purpose of this research was to develop an efficient method for the enantioselective construction of quaternary carbon stereocenters, which is a significant but challenging objective in organic chemistry. The researchers found that by choosing different ligands, they could control the regioselectivity of the reaction. Specifically, the use of (R)-H8-binap as a ligand led to the formation of 1,4-adducts with a quaternary stereocenter with high regio- and enantioselectivity. Key chemicals used in the process included arylboronic acids, substituted maleimides, and various ligands such as (R,R)-Bn-bod*, (R,R)-Ph-bod*, (R)-binap, and (R)-H8-binap. The study concluded that the ligand choice is crucial for controlling the regioselectivity, and the developed method provides a broad scope for the asymmetric construction of quaternary carbon stereocenters with high selectivity.
10.1016/0022-328X(90)85067-9
The research investigates the synthesis, reactions, and crystal structure of rhodium hydride complexes containing phosphite/phosphito ligands. The complex HRh{[P(OMe)2O]2H}2(CO) is of particular interest due to its metal hydride and acidic proton. The study explores the displacement of the carbonyl ligand by P-donor ligands and the replacement of bridging protons with BF3 groups. The complexes do not react with CO2 or CS2 but react with isocyanates to yield ureas and oligomers. The X-ray crystal structure of HRh{[P(OMe)2O]2H}2(PPh2Me) reveals a distorted octahedral structure with significant differences in the planarity of the phosphite/phosphito chelate rings, likely due to the orientation of phenyl groups in the PPh2Me ligand. The study also examines reactions with bidentate phosphines and heteroallenes like phenyl isocyanate, highlighting the reactivity differences between phosphite/phosphito and phosphinite/phosphinito ligands in Rh and Mo complexes.
F,
C,
Xi
F:Flammable;
