338800-13-8 | Page 2 of 9 | Pyridine-derivatives

Nerush, Alexander’s team published research in Journal of the American Chemical Society in 138 | CAS: 338800-13-8

Journal of the American Chemical Society published new progress about 338800-13-8. 338800-13-8 belongs to pyridine-derivatives, auxiliary class Bis-phosphine Ligands, name is 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, and the molecular formula is C23H43NP2, Category: pyridine-derivatives.

Nerush, Alexander published the artcileTemplate Catalysis by Metal-Ligand Cooperation. C-C Bond Formation via Conjugate Addition of Non-activated Nitriles under Mild, Base-free Conditions Catalyzed by a Manganese Pincer Complex, Category: pyridine-derivatives, the publication is Journal of the American Chemical Society (2016), 138(22), 6985-6997, database is CAplus and MEDLINE.

The first example of a catalytic Michael addition reaction of non-activated aliphatic nitriles to α,β-unsaturated carbonyl compounds under mild, neutral conditions is reported. A new de-aromatized pyridine-based PNP pincer complex of the Earth-abundant, first-row transition metal manganese serves as the catalyst. The reaction tolerates a variety of nitriles and Michael acceptors with different steric features and acceptor strengths. Mechanistic investigations including temperature-dependent NMR spectroscopy and DFT calculations reveal that the cooperative activation of alkyl nitriles, which leads to the generation of metalated nitrile nucleophile species (α-cyano carbanion analogs), is a key step of the mechanism. The metal center is not directly involved in the catalytic bond formation but rather serves, cooperatively with the ligand, as a template for the substrate activation. This approach of “template catalysis” expands the scope of potential donors for conjugate addition reactions.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

Lutz, Martin’s team published research in Polyhedron in 28 | CAS: 338800-13-8

Polyhedron published new progress about 338800-13-8. 338800-13-8 belongs to pyridine-derivatives, auxiliary class Bis-phosphine Ligands, name is 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, and the molecular formula is C23H43NP2, COA of Formula: C23H43NP2.

Lutz, Martin published the artcileA reversible solid-solid phase transition Z’=1 to Z’=6 in [Ni(OAc)(PNP^tBu)]OTf, COA of Formula: C23H43NP2, the publication is Polyhedron (2009), 28(12), 2341-2346, database is CAplus.

At ambient temperature, [Ni(OAc)(PNP^tBu)]OTf has one independent mol. in the asym. unit of the crystal structure with very large anisotropic displacement parameters. During cooling a fully reversible solid-solid phase transition occurs at a discrete temperature in the range 210-230 K The low-temperature phase has six independent, well ordered mols. in the asym. unit. The P2₁/a space group symmetry of the high-temperature phase changes to P2₁/n for the low-temperature phase and the c-axis increases by a factor of six. The acetate ligand is coordinated in a η ¹-fashion through one of the O atoms, with the sterically encumbered, tridentate PNP^tBu ligand completing the square planar geometry around the Ni^II ion. The synthesis and full characterization of the complex is reported. Crystallog. data are given.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

Stambuli, James P.’s team published research in Journal of the American Chemical Society in 123 | CAS: 338800-13-8

Stambuli, James P. published the artcileScreening of Homogeneous Catalysts by Fluorescence Resonance Energy Transfer. Identification of Catalysts for Room-Temperature Heck Reactions, Computed Properties of 338800-13-8, the publication is Journal of the American Chemical Society (2001), 123(11), 2677-2678, database is CAplus and MEDLINE.

The authors report a method to screen for transition metal-catalyzed reactions based on Fluorescence Resonance Energy Transfer (FRET) and the use of this assay to identify catalysts for room-temperature Heck reactions of aryl bromides.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

van der Vlugt, Jarl Ivar’s team published research in Organometallics in 28 | CAS: 338800-13-8

Organometallics published new progress about 338800-13-8. 338800-13-8 belongs to pyridine-derivatives, auxiliary class Bis-phosphine Ligands, name is 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, and the molecular formula is C20H40O2, COA of Formula: C23H43NP2.

van der Vlugt, Jarl Ivar published the artcileA Cationic Ag^I(PNP^tBu) Species Acting as PNP Transfer Agent: Facile Synthesis of Pd(PNP^tBu)(alkyl) Complexes and Their Reactivity Compared to PCP^tBu Analogues, COA of Formula: C23H43NP2, the publication is Organometallics (2009), 28(24), 7025-7032, database is CAplus.

The straightforward synthesis of cationic complex I, [Ag(PNP^tBu)]BF₄ (PNP^tBu = 1,2-bis[(di-tert-butylphosphino)methyl]pyridine), and its facile transmetalating properties toward gold and palladium are described. The corresponding Au complex [Au(PNP^tBu)]₂(BF₄)₂ (2) exists as a dimer in the solid state, as deduced by x-ray crystallog. The transmetalating properties were expanded to include the formation of Pd-alkyl species. Reaction of I with 0.5 equiv of Pd(allyl)(μ-Cl) dimer led to clean formation of the [Pd(PNP^tBu)(η¹-allyl)]BF₄ complex 3. The analogous cationic Me (4), cyanophenyl (5), and chloro species (6) could also be prepared in good yields from appropriate Pd precursors via this transmetalation methodol. The mol. structures for complexes 3–5 were established by x-ray crystallog. Reaction of complexes 4 and 6 with NaN(SiMe₃)₂ led to deprotonation and dearomatization of the PNP backbone with formation of the neutral Pd species 7 and 8, which can be regarded as the diphosphino-monoamido N-ligated analogs of well-studied Pd(PCP^tBu) complexes. These neutral Pd(PN^–P^tBu) complexes 7 and 8 displayed reasonable activity in the Suzuki-Miyaura coupling of phenylboronic acid pinacol ester and bromoarenes.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

Arashiba, Kazuya’s team published research in Organometallics in 31 | CAS: 338800-13-8

Arashiba, Kazuya published the artcileSynthesis and Protonation of Molybdenum- and Tungsten-Dinitrogen Complexes Bearing PNP-Type Pincer Ligands, Safety of 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, the publication is Organometallics (2012), 31(5), 2035-2041, database is CAplus.

Novel molybdenum- and tungsten-dinitrogen complexes bearing PNP-type pincer ligands are prepared and characterized by x-ray anal. Reactions of these molybdenum- and tungsten-dinitrogen complexes with an excess amount of sulfuric acid in THF at room temperature afford ammonia and hydrazine in good yields.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

Smith, Ashleigh D.’s team published research in Polyhedron in 114 | CAS: 338800-13-8

Smith, Ashleigh D. published the artcileSynthesis, characterization and reactivity of iron- and cobalt-pincer complexes, Related Products of pyridine-derivatives, the publication is Polyhedron (2016), 286-291, database is CAplus.

The ^tBuPONOP (2,6-bis(di-tert-butylphosphinito)pyridine) complexes of iron and cobalt, (^tBuPONOP)FeCl₂ (1) and (^tBuPONOP)CoCl₂ (2), were prepared Both complexes are paramagnetic and the solid-state structures of 1 and 2 were determined by single crystal x-ray diffraction studies. Analogous Fe and Co complexes of the ^tBuPNP (2,6-bis(di-tert-butyl-phosphinomethyl)pyridine) ligand (3 and 4, resp.) were prepared to allow comparison between the closely related pincer ligands in the hydrosilylation of carbonyl moieties. All four complexes are catalytically active when treated with NaBEt₃H, which was assumed to generate a metal-hydride species in-situ.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

Vogt, Matthias’s team published research in Organometallics in 32 | CAS: 338800-13-8

Vogt, Matthias published the artcileAnionic Nickel(II) Complexes with Doubly Deprotonated PNP Pincer-Type Ligands and Their Reactivity toward CO₂, Category: pyridine-derivatives, the publication is Organometallics (2013), 32(1), 300-308, database is CAplus.

The aromatization-dearomatization reaction of pincer-type complexes prompted by protonation-deprotonation of the pincer “arm” is a key step in bond activation chem. and atom-economic catalytic transformations. However, the possibility of double deprotonation of ancillary pincer ligands is rarely discussed in the literature. Here authors report on square-planar cationic nickel(II) complexes of PNP^R type ligands (PNP = 2,6-bis[(dialkylphosphino)methyl]pyridine with R = ⁱPr, ^tBu), which can be readily transformed into the doubly deprotonated anionic species. The complexes [Ni(PNP^R)Cl]Cl (3, R = ⁱPr; 4, R = ^tBu) are readily prepared from the reaction of NiCl₂·6H₂O and the PNP^R ligand in THF. Treatment of the cationic chloro complexes 3 and 4 with 2 equivalent of MeLi gives the nickel(II) Me complexes [Ni(PNP^R*)Me] (7, R = ⁱPr; 8, R = ^tBu), the asterisk indicates the deprotonated pincer arm. Reaction of 7 and 8 with an addnl. 1 equivalent of MeLi gives the anionic complexes [Li(DME)₃][Ni(PNP^iPr**)Me] (9-DME, DME = 1,2-dimethoxyethane) and [Li(Et₂O)₂][Ni(PNP^tBu**)(Me)] (10-Et₂O), resp. Single-crystal x-ray diffraction studies exhibit doubly deprotonated PNP-pincer ligands coordinated to a nickel(II) center. DFT calculations, as well as multinuclear NMR spectroscopy and the x-ray structures, suggest a conjugated π-system with delocalization of the neg. charge throughout the carbon backbone of the pincer ligand. The electrophilic attack of complex 9 by CO₂ and tautomerization gives [Li][Ni(PNP^iPr*-COO)(Me)] (11). The dearomatized complex that is formed contains an exocyclic methylene carbon atom and a carboxylate moiety adjacent to the second pincer arm.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

Li, Zhehui’s team published research in Journal of the American Chemical Society in 140 | CAS: 338800-13-8

Li, Zhehui published the artcileAperture-Opening Encapsulation of a Transition Metal Catalyst in a Metal-Organic Framework for CO₂ Hydrogenation, HPLC of Formula: 338800-13-8, the publication is Journal of the American Chemical Society (2018), 140(26), 8082-8085, database is CAplus and MEDLINE.

The aperture-opening process resulting from dissociative linker exchange in zirconium-based metal-organic framework (MOF) UiO-66 was used to encapsulate the ruthenium complex (^tBuPNP)Ru(CO)HCl in the framework (^tBuPNP = 2,6-bis((di-tert-butyl-phosphino)methyl)pyridine). The resulting encapsulated complex, [Ru]@UiO-66, was a very active catalyst for the hydrogenation of CO₂ to formate. Unlike the analogous homogeneous catalyst, [Ru]@UiO-66 could be recycled five times, showed no evidence for bimol. catalyst decomposition, and was less prone to catalyst poisoning. These results demonstrated for the first time how the aperture-opening process in MOFs can be used to synthesize host-guest materials useful for chem. catalysis.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

Gair, Joseph J.’s team published research in Organometallics in 38 | CAS: 338800-13-8

Gair, Joseph J. published the artcileSynthesis, Characterization, and Theoretical Investigation of a Transition State Analogue for Proton Transfer during C-H Activation by a Rhodium-Pincer Complex, COA of Formula: C23H43NP2, the publication is Organometallics (2019), 38(7), 1407-1412, database is CAplus.

A heterobimetallic Rh-pincer complex bearing a phenylzinc ligand was synthesized and characterized by multinuclear NMR, COSY, NOESY, and x-ray crystallog. The crystal structure of this complex shows that it possesses a bridging Rh-Zn-C fragment with a geometry similar to the Rh-H-C fragment in a proposed transition state for metal to ligand proton transfer during redox-neutral C-H activation with dearomatized Rh pincer complexes. Bonding anal. indicates that these fragments are isolobal, suggesting that the transition state analog models not only the structure but also the bonding interactions that underlie metal-ligand cooperativity in the C-H activation transition state. The similarity of the transition state and its analog prompted reevaluation of the relevant rate equations to determine the relative contributions of viable proton transfer pathways. Parallel anal. of the transition state and its isolobal analog thus serves as a bridge between theory and experiment that is rarely available in studies of bonding in transition states.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem

van der Vlugt, Jarl Ivar’s team published research in Inorganic Chemistry in 48 | CAS: 338800-13-8

Inorganic Chemistry published new progress about 338800-13-8. 338800-13-8 belongs to pyridine-derivatives, auxiliary class Bis-phosphine Ligands, name is 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, and the molecular formula is C10H11NO4, Recommanded Product: 2,6-Bis((di-tert-butylphosphino)methyl)pyridine.

van der Vlugt, Jarl Ivar published the artcileCu^I Complexes with a Non-innocent PNP Ligand: Selective Dearomatization and Electrophilic Addition Reactivity, Recommanded Product: 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, the publication is Inorganic Chemistry (2009), 48(16), 7513-7515, database is CAplus and MEDLINE.

The neutral, T-shaped complex Cu^I(PN^–P^tBu) (2)featuring a de-aromatized 2,6-bis[(di-tert-butylphosphino)methyl]pyridine (PN^–P^tBu) PNP-pincer ligand, is shown to interact rapidly with electrophiles. Furthermore, C-C bond formation onto the deprotonated methylene-bridgehead carbon is observed with MeOTf as the electrophile. The mol. structure of the methylated derivatives were determined by X-ray crystallog. This represents the first case of selective modification of the lutidine-based backbone of such non-innocent PNP ligands. Theor. calculations support the formation of monomeric complex 2 and indicate the high reactivity of the methylene fragment in this Cu^I complex.

Referemce:
https://en.wikipedia.org/wiki/Pyridine,
Pyridine | C5H5N – PubChem