The electron-rich pincer ligand 1 has been synthesized and chelated to manganese. The octahedral Mn(iv) bis(diiminosemiquinonate) and Mn(v) (diiminobenzoquinone) (diiminosemiquinonate) radicals were structurally characterized.
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Synthesis and characterization of heptacoordinated molybdenum(II) complexes supported with 2,6-bis(pyrazol-3-yl)pyridine (bpp) ligands.
Dalton Trans
January 2025
LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 route de Narbonne, BP44099 F-31077 Toulouse cedex 4, France.
Functional pincer ligands that engage in metal-ligand cooperativity and/or are capable of redox non-innocence have found a great deal of success in catalysis. These two properties may be found in metal complexes of the 2,6-bis(pyrazol-3-yl)pyridine (bpp) ligands. With this goal in mind, we have attempted the coordination of 2,6-bis(5-trifluoromethylpyrazol-3-yl)pyridine (LCF3) and its Bu analogue 2,6-bis(5--butylpyrazol-3-yl)pyridine (LtBu) to Mo(0) by reactions with mixed phosphine/carbonyl complexes [Mo(CO)(MeCN)(PMePh)] 1-3 (1 ≤ ≤ 3).
View Article and Find Full Text PDFCatalysis activity and chemoselectivity control with the ligand in Ru-H pincer complexes.
Dalton Trans
January 2025
Division of Chemical and Biological Sciences, Ames National Laboratory, Ames, IA 50011, USA.
(PhPNP)Ru(H)(Cl)(CO) serves as a precatalyst to a variety of important catalytic transformations but most improvements have been restricted to the replacement of the CO ligand to the hydride or changing the Ph groups of the pincer for other aryl or alkyl groups. The ligand to the hydride is often another hydride and studies that utilize other ligands in catalysis are limited. In this work, we synthesized a series of [(PhPNP)Ru(H)(CO)(L)][BPh] complexes bearing isonitrile, PMe, or a N-heterocyclic ligand to the Ru-H.
View Article and Find Full Text PDFUnlocking CO2 Activation with A Novel Ni-Hg-Ni Trinuclear Complex.
Angew Chem Int Ed Engl
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CNRS: Centre National de la Recherche Scientifique, Chemistry, FRANCE.
Compounds featuring bonds between mercury and transition metals are of interest for their intriguing/ambiguous bonding and scarcely explored reactivities. We report herein the synthesis and reactivities of the new compound [(POCOP)Ni]2Hg, [Ni2Hg], featuring a trinuclear Ni-Hg-Ni core (POCOP = κP,κC,κP´-2,6-(i-Pr2PO)2C6H3). [Ni2Hg] reacts with CO2 to give the carbonate-bridged complex [Ni2CO3].
View Article and Find Full Text PDFAccess to Bis-Silylene-Stabilized Group 13 Cations.
Inorg Chem
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Department of Chemistry, Indian Institute of Science Education and Research Pune, Dr. Homi Bhabha Road, Pashan, Pune 411008, India.
Herein, we report the isolation of pyridine moiety-functionalized SiNSi pincer-based bis-silylene ligand () and its reactivity toward various halide precursors (X = Br and I) of group 13 elements (M = Al, Ga, and In). This gave us straightforward access to the SiNSi pincer-coordinated group 13 cations (-). These complexes are duly characterized by single-crystal X-ray diffraction studies, multinuclear magnetic resonance spectroscopy (H, C, and Si), and high-resolution mass spectrometry techniques.
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Angew Chem Int Ed Engl
January 2025
Martin-Luther-Universitat Halle-Wittenberg, Department of Chemistry, Kurt-Mothes-Str. 2, 06120, Halle, GERMANY.
A pronounced nucleophilicity in combination with a distinct redox non-innocence is a unique feature of a coordinated ligand, which in the current case, leads to unprecedented carbon-centered reactivity patterns: A carbodiphosphorane-based (CDP) pincer-type rhodium complex allows to cleave two C-Cl-bonds of geminal dichlorides via two consecutive SN2-type oxidative additions resulting in the formation of a stabilized carbene fragment. In the presence of a suitable reductant the carbene fragment can even be converted into olefines or hydrodehalogenation products in a catalytic reaction. The developed method can also be used to convert chlorofluorocarbons (CFCs) such as CH2ClF to fluoromethane and methane.
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