This work documents the first palladium pincer complex-catalyzed carbonylative Sonogashira (CS) and carbonylative Suzuki-Miyaura (CSM) cross-coupling. Compared to previous protocols, which employ hazardous and toxic solvents, the aminophosphine pincer complex {[CH-2,6-(NHP{piperidinyl})]Pd(Cl)} () catalyzes both the cross-coupling reactions in propylene carbonate, an eco-friendly and sustainable polar aprotic solvent. Advantageously, employing allows the CS cross-coupling to be carried out at a palladium loading of 10 mol % and the CSM cross-coupling to be carried out at 10 mol %, thus resulting in catalytic turnovers of 10 and 10, respectively. Relative comparison of the pincer complex with conventional palladium precursors Pd(OAc) and PdCl(PPh) shows the efficiency and robustness of the pincer complex in effecting higher catalytic activity at low palladium loadings.
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http://dx.doi.org/10.1021/acsomega.8b02886 | DOI Listing |
Nat Chem
January 2025
Instituto de Investigaciones Químicas, Consejo Superior de Investigaciones Científicas and Universidad de Sevilla, Sevilla, Spain.
Open-shell systems based on first-row transition metals and their involvement in various catalytic processes are well explored. By comparison, mononuclear open-shell complexes of precious transition metals remain underdeveloped. This is particularly true for Ir complexes, as there is very limited information available regarding their application in catalysis.
View Article and Find Full Text PDFInorg Chem
January 2025
Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, United States.
A Pt(II) aqua complex supported by mesoporous silica nanoparticle (MSN)-immobilized sulfonated CNN pincer ligand featuring a rigid SiO tether was prepared. This hybrid material was tested as a catalyst in H/D exchange reactions of C(sp)-H bonds of selected aromatic substrates and DO-2,2,2-trifluoroethanol- (TFE-) mixtures or CDCOD acting as a source of exchangeable deuterium. The catalyst immobilization served as a means to not only enable the catalyst's recyclability but also minimize the coordination of sulfonate groups and the metal centers originating from different catalyst's moieties that would preserve reactive Pt(OH) fragments needed for catalytic C-H bond activation.
View Article and Find Full Text PDFOrganometallics
January 2025
Department of Chemistry, Texas A&M University, 3255 TAMU, College Station, Texas 77842, United States.
Protolysis of AlMe or AlEt with 2-diisopropylphosphinopyrrole () resulted in alane/bis(phosphine) pincer ligands containing two flanking phosphines and a central Al-Me (), Al-Et () unit. Reactions of with [(COD)MI] (COD = 1,5-cyclooctadiene; M = Rh or Ir) in the presence of pyridine produced pincer complexes ( and ) with M supported by the PAlP tridentate ligand, and pyridine, methyl, and iodide as monodentate ligands for Al or M. The analogous reaction of with [(COD)MI] and pyridine resulted in the formation of the analogous compounds and with hydride in place of methyl.
View Article and Find Full Text PDFOrganometallics
January 2025
Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Faculty of Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands.
We report the synthesis and characterization of a series of high- and low-spin dicobalt complexes of the PNNP expanded pincer ligand. Reacting this dinucleating ligand in its neutral form with two equiv of CoCl(tetrahydrofuran) yields a high-spin dicobalt complex featuring one Co inside and one Co outside of the dinucleating pocket. Performing the same reaction in the presence of two equivalents of KOtBu provides access to a high-spin dicobalt complex wherein both Co centers are bound within the PNNP pocket, and this complex also features a bridging OtBu ligand.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department for Chemistry, Technical University of Denmark (DTU), 2800 Kongens Lyngby, Denmark.
A new Ru(II) complex featuring a novel amino-di(N-heterocyclic carbene) CNC pincer ligand, CNC-RuCl(CO) (Ru-1), has been developed and characterised in depth. Ru-1 forms an efficient and durable catalytic formic acid dehydrogenation system in combination with the ionic liquid 1-ethyl-3-methylimidazolium diethylphosphate (EMIM PO(OEt)).
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