Category: 338800-13-8

Simler, Thomas published the artcilePotassium and Lithium Complexes with Monodeprotonated, Dearomatized PNP and PNC^NHC Pincer-Type Ligands, Product Details of C23H43NP2, the publication is Organometallics (2016), 35(6), 903-912, database is CAplus.

The reaction of 2,6-bis(di-tert-butylphosphinomethyl)pyridine (^tBuPN^tBuP) with 1 molar equiv of KCH₂C₆H₅ or LiCH₂SiMe₃ gave M(^tBuP^*N_a^tBuP) (M = K, Li; P^* = vinylic P donor, ^tBuP = P^tBu₂, N_a = anionic amido N donor) after monodeprotonation of the α-lutidinyl-CH₂ and concomitant dearomatization of the heterocycle. Evidence is provided that the anion ^tBuP^*N_a^tBuP may exist as Z- and E-isomers, interconvertible by rotation about the C_α-N-C_α-P exocyclic formal double bond. Thus, the two isomers of K(^tBuP^*N_a^tBuP), i.e., [K{(Z)-(^tBuP^*N_a^tBuP-κP^*,κN_a,κP)}(THF)], 1-Z·(THF), and [K{(E)-(^tBuP^*N_a^tBuP-κN_a,κP)}(THF)], 1-E·(THF), cocrystd. from THF in a 4:1 ratio. However, in the presence of DME, the isomerically pure [K{(E)-(^tBuP^*N_a^tBuP-κN_a,κP)}(DME)₂], 1-E·2(DME), was crystallized The α-picolinyl-CH₂ moiety in ^RPNC^NHC (N = substituted 2-picoline, ^RP = PCy₂, R = Cy; ^RP = P^tBu₂, R = ^tBu; C^NHC = N-heterocyclic carbene) was similarly deprotonated with concomitant dearomatization using LiN(SiMe₃)₂. This afforded the complexes Li(^RP^*N_aC^NHC), which were crystallized as the Z- or E-isomers, [Li{(E)-(^tBuP^*N_aC^NHC-κN_a,κC^NHC)}(Et₂O)₂], 3^tBu-E·2(Et₂O), [Li{(Z)-(^CyP^*N_aC^NHC-κP^*,κN_a,κC^NHC)}(Et₂O)], 3^Cy-Z·(Et₂O), and [Li{(Z)-(^tBuP^*N_aC^NHC-κP^*,κN_a,κC^NHC)}(Et₂O)], 3^tBu-Z·(Et₂O). The Z- and E-isomers reversibly interconvert in solution as shown by ³¹P{¹H} and ⁷Li NMR spectroscopy. The acidity of the α-picolinyl-CH₂ in ^RPNC^NHC is higher than in the known ^tBuPN^tBuP (ca. by 6 pK_a units).

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 C3H9ClOS, Product Details of C23H43NP2.

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

Rauch, Michael published the artcileMetal-Ligand Cooperation Facilitates Bond Activation and Catalytic Hydrogenation with Zinc Pincer Complexes, COA of Formula: C23H43NP2, the publication is Journal of the American Chemical Society (2020), 142(34), 14513-14521, database is CAplus and MEDLINE.

A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facilitating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals. Safety: caution advised with pyrophoric organozinc compounds, gas evolution at high temperature and reactions involving H₂.

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, COA of Formula: C23H43NP2.

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

Smoll, Karena A. published the artcilePhotolysis of Pincer-Ligated Pd^II-Me Complexes in the Presence of Molecular Oxygen, Application In Synthesis of 338800-13-8, the publication is Organometallics (2017), 36(7), 1213-1216, database is CAplus.

The reactions of ^t-BuPNP and ^t-BuPCP Pd^II-Me complexes (^t-BuPNP = 2,6-bis[(di-tert-butylphosphino)methyl]pyridine and ^t-BuPCP = 2,6-bis[(di-tert-butylphosphino)methyl]phenyl) with O₂ are described and compared with the reported O₂ reactivity of related Pd^II-Me complexes. [(^t-BuPNP)PdMe]Cl was found to react with O₂ upon photolysis resulting in oxidation of the pincer ligand backbone to produce a (^t-BuPNO)PdCl complex. In contrast, photolysis of (^t-BuPCP)PdMe with O₂ resulted in oxidation of the Pd-Me group to form (^t-BuPCP)PdOCO₂H. Isotopic labeling, radical initiators, and solvent studies were used to gain insight into the mechanisms of these unusual reactions of late metal alkyls with mol. oxygen.

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 C7H7ClN2S, Application In Synthesis of 338800-13-8.

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

Shaffer, David W. published the artcileReactivity of a Series of Isostructural Cobalt Pincer Complexes with CO₂, CO, and H⁺, Product Details of C23H43NP2, the publication is Inorganic Chemistry (2014), 53(24), 13031-13041, database is CAplus and MEDLINE.

The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)₂P^EPy^EP(t-Bu)₂(MeCN)₂][BF₄]₂ (Py = pyridine, E = CH₂, NH, O, and X = BF₄ (1a–c)) and the corresponding one-electron reduced analogs [Co(t-Bu)₂P^EPy^EP(t-Bu)₂(MeCN)][BF₄] (2a–c) are reported. The reactivity of the reduced cobalt complexes with CO₂, CO, and H⁺ to generate intermediates in a CO₂ reduction to CO and H₂O cycle are described. The reduction of 1a–c and subsequent reactivity with CO₂ was investigated by cyclic voltammetry, and for 1a also by IR spectroelectrochem. The corresponding CO complexes of (2a–c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mech. methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H⁺ vs. CO₂. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.

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 C9H10O4, Product Details of C23H43NP2.

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

Hu, Gongfang published the artcileSurprisingly big linker-dependence of activity and selectivity in CO₂ reduction by an iridium(I) pincer complex, Formula: C23H43NP2, the publication is Chemical Communications (Cambridge, United Kingdom) (2020), 56(64), 9126-9129, database is CAplus and MEDLINE.

Here, we report the quant. electroreduction of CO₂ to CO by a PNP-pincer iridium(I) complex bearing amino linkers in DMF/water. The electrocatalytic properties greatly depend on the choice of linker within the ligand. The complex 3-N is far superior to the analogs with methylene and oxygen linkers, showing higher activity and better selectivity for CO₂ over proton reduction

Chemical Communications (Cambridge, United Kingdom) 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, Formula: C23H43NP2.

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

Fogler, Eran published the artcileRu(0) and Ru(II) Nitrosyl Pincer Complexes: Structure, Reactivity, and Catalytic Activity, Product Details of C23H43NP2, the publication is Inorganic Chemistry (2013), 52(19), 11469-11479, database is CAplus and MEDLINE.

Despite considerable interest in ruthenium carbonyl pincer complexes and their substantial catalytic activity, there has been relatively little study of the isoelectronic ruthenium nitrosyl complexes. Here the authors describe the synthesis and reactivity of several complexes of this type as well as the catalytic activity of complex 6. Reaction of the PNP ligand (PNP = 2,6-bis(^tBu₂PCH₂)pyridine) with RuCl₃(NO)(PPh₃)₂ yielded the Ru(II) complex 3. Chloride displacement by BAr^F- (BAr^F- = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) gave the crystallog. characterized, linear NO Ru(II) complex 4, which upon treatment with NaBEt₃H yielded the Ru(0) complexes 5. The crystallog. characterized Ru(0) square planar complex 5·BF₄ bears a linear NO ligand located trans to the pyridyl nitrogen. Further treatment of 5·BF₄ with excess LiOH gave the crystallog. characterized Ru(0) square planar, linear NO complex 6. Complex 6 catalyzes the dehydrogenative coupling of alcs. to esters, reaching full conversion under air or under argon. Reaction of the PNN ligand (PNN = 2-(^tBu₂PCH₂)-6-(Et₂NCH₂)pyridine) with RuCl₃(NO)(H₂O)₂ in ethanol gave an equilibrium mixture of isomers 7a and 7b. Further treatment of 7a + 7b with 2 equiv of sodium isopropoxide gave the crystallog. characterized, bent-nitrosyl, square pyramidal Ru(II) complex 8. Complex 8 was also synthesized by reaction of PNN with RuCl₃(NO)(H₂O)₂ and Et₃N in ethanol. Reaction of the “long arm” PN²N ligand (PN²N = 2-(^tBu₂PCH₂)-6-(Me₂NCH₂CH₂)pyridine) with RuCl₃(NO)(H₂O)₂ in ethanol gave complex 9, which upon treatment with 2 equiv of sodium isopropoxide gave complex 10. Complex 10 was also synthesized directly by reaction of PN²N with RuCl₃(NO)(H₂O)₂ and a base in ethanol. A noteworthy aspect of these nitrosyl complexes is their preference for the Ru(0) oxidation state over Ru(II). This preference is observed with both aromatized and dearomatized pincer ligands, in contrast to the Ru(II) oxidation state which is preferred by the analogous carbonyl complexes.

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 C23H43NP2, Product Details of C23H43NP2.

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

Goncalves, Theo P. published the artcileMetal-Ligand Cooperative Reactivity in the (Pseudo)-Dearomatized PN^x(P) Systems: The Influence of the Zwitterionic Form in Dearomatized Pincer Complexes, SDS of cas: 338800-13-8, the publication is Journal of the American Chemical Society (2017), 139(38), 13442-13449, database is CAplus and MEDLINE.

The concept of aromaticity in pincer ligands and complexes was discussed in order to provide insights into their metal-ligand cooperative activities. The aromatic PN^x(P) and dearomatized PN^x(P)* pincer ligands and the corresponding transition metal complexes were studied with the nucleus-independent chem. shift (NICS_zz), anisotropy of the current (induced) d. (ACID), isochem. shielding surfaces (ICSS_zz), harmonic oscillator model of aromaticity (HOMA), MCBO, Shannon aromaticity, and natural bond order (NBO) analyses. The study on the model systems showed that for the dearomatized species the decrease of the NICS(1)_zz value comes with the larger contribution of the aromatic zwitterionic mesomeric form. In all examples, the incorporation of the metal center into the pincer ligand decreases the NICS(1)_zz values. The DFT calculations support the dearomatized pyridine ring in PNP* or PNN* ligand indeed being nonaromatic, in contrast to the PN³(P)* ligand which has partial aromatic character due to the larger contribution of the zwitterionic resonance structure. The difference in aromaticity between the rings contributes to the thermodn. balance of the metal ligand cooperative reactions, changing the energetics of the process when different dearomatized pincer ligands are used. This was further exemplified by aromaticity anal. of the heterolytic hydrogen cleavage reaction of ruthenium PNN complexes of Milstein and the PN³ of Huang, with similar geometries but distinctive thermodn. preference.

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, SDS of cas: 338800-13-8.

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

Hanson, Susan Kloek published the artcileC-H Bond Activation by Rhodium(I) Phenoxide and Acetate Complexes: Mechanism of H-D Exchange between Arenes and Water, HPLC of Formula: 338800-13-8, the publication is Organometallics (2008), 27(7), 1454-1463, database is CAplus.

New rhodium(I) complexes (PNP)Rh(X) (PNP = 2,6-bis(di-tert-butylphosphinomethyl)pyridine) (X = OTf (1), OAc (3), OH (8), OCH₂CF₃ (9), OC₆H₅ (10), OC₆H₄NO₂ (11)) have been prepared Hydroxide complex 8 and trifluoroethoxide complex 9 undergo stoichiometric activation of benzene-d₆ to form the Ph complex (PNP)Rh(C₆D₅). Acetate and aryloxide complexes 3, 10, and 11 are active catalysts for H-D exchange between arenes and water. Control experiments indicate that the rhodium complexes are the active catalysts and that the observed exchange is not catalyzed by adventitious acid. Mechanistic studies of the H-D exchange reaction support a pathway involving dissociation of aryloxide or acetate ligand. The reaction is accelerated by added alc. and, for the acetate complex, inhibited by added sodium acetate.

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 C23H43NP2, HPLC of Formula: 338800-13-8.

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

Doyle, Laurence R. published the artcileA Convenient Synthetic Protocol to 1,2-Bis(dialkylphosphino)ethanes, COA of Formula: C23H43NP2, the publication is Advanced Synthesis & Catalysis (2014), 356(2-3), 603-608, database is CAplus and MEDLINE.

1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel NaAlH₄/NaH reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, uses readily available and inexpensive reagents, and benefits from a facile nonaqueous work-up in the final reductive step.

Advanced Synthesis & Catalysis 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.

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

Kloek, Susan M. published the artcileC-H bond activation by rhodium(I) hydroxide and phenoxide complexes, Related Products of pyridine-derivatives, the publication is Angewandte Chemie, International Edition (2007), 46(25), 4736-4738, database is CAplus and MEDLINE.

Rhodium(I) complexes of the form [(PNP)Rh(OR)](R = H, CH₂CF₃, C₆H₅; PNP = 2,6-bis[(di-tert-butylphosphino)-methyl]pyridine) have been prepared Upon thermolysis in [D₆]benzene, the hydroxide and trifluoroethoxide complexes undergo benzene activation. [(PNP)Rh(OC₆H₅)] is an active catalyst for the H/D exchange between D₂O and benzene and between H₂O and [D₈]toluene, for which exchange occurs selectively at the meta and para positions.

Angewandte Chemie, International Edition 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, Related Products of pyridine-derivatives.

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