Dataset Information

Catalytic Behavior of Mono-N-Protected Amino-Acid Ligands in Ligand-Accelerated C-H Activation by Palladium(II).

ABSTRACT: Mono-N-protected amino acids (MPAAs) are increasingly common ligands in Pd-catalyzed C-H functionalization reactions. Previous studies have shown how these ligands accelerate catalytic turnover by facilitating the C-H activation step. Here, it is shown that MPAA ligands exhibit a second property commonly associated with ligand-accelerated catalysis: the ability to support catalytic turnover at substoichiometric ligand-to-metal ratios. This catalytic role of the MPAA ligand is characterized in stoichiometric C-H activation and catalytic C-H functionalization reactions. Palladacycle formation with substrates bearing carboxylate and pyridine directing groups exhibit a 50-100-fold increase in rate when only 0.05 equivalents of MPAA are present relative to Pd^II . These and other mechanistic data indicate that facile exchange between MPAAs and anionic ligands coordinated to Pd^II enables a single MPAA to support C-H activation at multiple Pd^II centers.

SUBMITTER: Salazar CA

PROVIDER: S-EPMC7311301 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Publications

Catalytic Behavior of Mono-N-Protected Amino-Acid Ligands in Ligand-Accelerated C-H Activation by Palladium(II).

Salazar Chase A CA Gair Joseph J JJ Flesch Kaylin N KN Guzei Ilia A IA Lewis Jared C JC Stahl Shannon S SS

Angewandte Chemie (International ed. in English) 20200408 27

Mono-N-protected amino acids (MPAAs) are increasingly common ligands in Pd-catalyzed C-H functionalization reactions. Previous studies have shown how these ligands accelerate catalytic turnover by facilitating the C-H activation step. Here, it is shown that MPAA ligands exhibit a second property commonly associated with ligand-accelerated catalysis: the ability to support catalytic turnover at substoichiometric ligand-to-metal ratios. This catalytic role of the MPAA ligand is characterized in st ...[more]

PMID: 32196853

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Project description:The series of complexes [XRu(CO)(L-L)(L')2][PF6] (X = H, TFA, Cl; L-L = 2,2'-bipyridyl, 1,10-phenanthroline, 5-amino-1,10-phenanthroline and 4,4'-dicarboxylic-2,2'-bipyridyl; L'2 = 2PPh3, Ph2 PC2H4PPh2, Ph2PCH═CHPPh2) have been synthesized from the starting complex K[Ru(CO)3(TFA)3] (TFA = CF3CO2) by first reacting with the phosphine ligand, followed by reaction with the L-L and anion exchange with NaPF6. In the case of L-L = phenanthroline and L'2 = 2PPh3, the neutral complex Ru(Ph3P)(CO)(1,10-phenanthroline)( TFA)2 is also obtained and its solid state structure is reported. Solid state structures are also reported for the cationic complexes where L-L = phenanthroline, L2 = 2PPh3 and X = Cl and for L-L = 2,2'-bipyridyl, L2 = 2PPh3 and X = H. All the complexes were characterized in solution by a combination of 1H and 31P NMR, IR, mass spectrometry and elemental analyses. The purpose of the project was to synthesize a series of complexes that exhibit a range of excited-state lifetimes and that have large Stokes shifts, high quantum yields and high intrinsic polarizations associated with their metal-to-ligand charge-transfer (MLCT) emissions. To a large degree these goals have been realized in that excited-state lifetimes in the range of 100 ns to over 1 μs are observed. The lifetimes are sensitive to both solvent and the presence of oxygen. The measured quantum yields and intrinsic anisotropies are higher than for previously reported Ru(II) complexes. Interestingly, the neutral complex with one phosphine ligand shows no MLCT emission. Under the conditions of synthesis some of the initially formed complexes with X = TFA are converted to the corresponding hydrides or in the presence of chlorinated solvents to the corresponding chlorides, testifying to the lability of the TFA Ligand. The compounds show multiple reduction potentials which are chemically and electrochemically reversible in a few cases as examined by cyclic voltammetry. The relationships between the observed photophysical properties of the complexes and the nature of the ligands on the Ru(II) is discussed.

Dataset Information

Catalytic Behavior of Mono-N-Protected Amino-Acid Ligands in Ligand-Accelerated C-H Activation by Palladium(II).

Publications

Catalytic Behavior of Mono-N-Protected Amino-Acid Ligands in Ligand-Accelerated C-H Activation by Palladium(II).

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