Category: 338800-13-8

Lease, Nicholas published the artcilePNP-Pincer Complexes of Osmium: Comparison with Isoelectronic (PCP)Ir and (PNP)Ir⁺ Units, SDS of cas: 338800-13-8, the publication is Organometallics (2018), 37(3), 314-326, database is CAplus.

Several complexes of (^tBu4PNP)Os (1, ^tBu4PNP = C₅NH₃-2,6-(CH₂P^tBu₂)₂) are reported. 1 Is isoelectronic with (^tBu4PCP)Ir (2, (^tBu4PCP)Ir = κ³-C₆H₃-2,6-(CH₂P^tBu₂)₂) which has played a leading role in homogeneous catalytic alkane dehydrogenation; the (^tBu4PNP)Os complexes were studied in this context. (^tBu4PNP)OsH₄ (1-H4) is analogous to (^tBu4PCP)IrH₄ (2-H4), but while 2-H4 has some character of a dihydrogen dihydride, 1-H4 is unambiguously a tetrahydride. Ethylene reacts with 1-H4 to afford trans-(^tBu4PNP)OsH₂(C₂H₄) (1-H₂(C₂H₄)). At 25°, 1-H₂(C₂H₄) readily undergoes reversible ethylene insertion into an Os-H bond to yield (^tBu4PNP)OsH(C₂H₅) (1-EtH). DFT calculations indicate that alkane C-H addition to 1 is thermodynamically much more favorable than addition to 2. The favorable thermodn. of 1-(alkyl)H, however, disfavor reductive elimination and formation of the free Os(0) fragment that is required for a catalytic cycle analogous to that reported for 2. C-H or H-H addition to 1 is much more favorable than to 2; this would typically be attributed to the lower oxidation state of 1. However, H₂ addition to the isoelectronic [(^tBu4PNP)Ir(I)]⁺ cation is even more favorable than addition to 1; thus the thermodn. differences result from the difference of the pincer ligand (PNP vs. PCP) rather than the different metal centers (Os(0) vs. Ir(I)). Although H₂ addition to Ir(I) is as favorable as addition to Os(0), addition of a 2nd mol. of H₂ (to give tetrahydrides) is much more favorable for (^tBu4PNP)Os. NBO anal. indicates that the MH₂/MH₄ additions are oxidative whereas the M/MH₂ transformations are reductive.

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, SDS of cas: 338800-13-8.

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

van der Vlugt, Jarl Ivar published the artcileDinuclear Copper(I) Thiolate Complexes with a Bridging Noninnocent PNP Ligand, Application of 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, the publication is Chemistry – A European Journal (2011), 17(14), 3850-3854, database is CAplus and MEDLINE.

The synthesis and crystal structures of dinuclear copper(I) complexes [Cu₂(μ-SR)(μ-PNP)Br] [R = Ph (4), CH₂Ph (5); PNP = 2,6-bis(di-tert-butylphosphinomethyl)pyridine] in which both the thiolate and PNP act as bridging ligands are described. The PNP ligand bridges in an unprecedented κ²-P,N-κ¹-P mode. The Cu…Cu distance of 2.7 Å, DFT calculations for optimized mol. structure, topol. anal. of electron d. in the framework of quantum theory of atoms in mols. (QT AIM) and natural-bond-order (NBO) anal. all indicate the absence of metallophilic interactions. These dinuclear complexes were prepared by treating a coordination polymer [Cu₂(μ-PNP)(μ-Br)₂]_n (3Br) with NaN(TMS)₂ followed by the thiol (HSR). The synthesis of the precursor 3Br from PNP and [CuBr(SMe₂)] is also described. The crystal structure of the related μ-chloro complex (3Cl) was determined since the μ-bromo complex formed poor quality crystals. Preliminary reactivity studies showed that the bromide ligand in complex 5 can be substituted with NCS or SPh.

Chemistry – A European Journal 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 C15H14Cl2S2, Application of 2,6-Bis((di-tert-butylphosphino)methyl)pyridine.

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

van der Vlugt, Jarl Ivar published the artcileT-Shaped Cationic Cu^I Complexes with Hemilabile PNP-Type Ligands, Quality Control of 338800-13-8, the publication is Inorganic Chemistry (2008), 47(11), 4442-4444, database is CAplus and MEDLINE.

The versatile coordination behavior of the PNP ligands 1A (2,6-bis[(di-tert-butylphosphino)methyl]pyridine) and 1B (2,6-bis[(diphenylphosphino)methyl]pyridine) to Cu^I is described. A hemilabile interaction of the pyridine N-donor atom to the Cu center resulted in a rare T-shaped complex with 1A, while with 1B also a tetracoordinated species could be isolated. Theor. calculations support the weak interaction of the pyridine N donor in 1A with the Cu center.

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 C4Br2N2O4S, Quality Control of 338800-13-8.

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

Gibson, Dorothy H. published the artcileSynthesis and Characterization of Ruthenium(II) Hydrido and Hydroxo Complexes Bearing the 2,6-Bis(di-tert-butylphosphinomethyl)pyridine Ligand, Related Products of pyridine-derivatives, the publication is Organometallics (2004), 23(10), 2510-2513, database is CAplus.

The reaction of [Ru(CO)₂Cl₂]_n with 2,6-bis(di-tert-butylphosphinomethyl)pyridine (PNP) and then anion exchange yields [Ru(PNP)(CO)₂Cl]PF₆ (1). Reaction of 1 with AgBF₄, in acetone, followed by MeCN and then anion exchange gave [Ru(PNP)(CO)₂(MeCN)](PF₆)₂ (2); reaction of 2 with H₂O gave [Ru(PNP)(CO)₂OH]PF₆ (3), whereas reaction of 2 with aqueous KOH led to [Ru(PNP)(CO)(MeCN)H]PF₆ (4). Complexes 3 and 4 were characterized by x-ray crystal structure anal.

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, Related Products of pyridine-derivatives.

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

Lokare, Kapil S. published the artcileIridium complexes bearing a PNP ligand, favoring facile C(sp³)-H bond cleavage, Application In Synthesis of 338800-13-8, the publication is Dalton Transactions (2011), 40(36), 9094-9097, database is CAplus and MEDLINE.

Hydrogen iodide is lost upon reaction of PNP with IrI₃, where PNP = 2,6-bis(di-t-butylphosphinomethyl)pyridine to give crystallog. characterized iridacycle Ir(PNP)^*(I)₂, which reacts with H₂ to give Ir(PNP)(H)(I)₂. Ir(PNP)(Cl)₃ is relatively inert towards the intramol. C-H activation of the tert-butyl’s of the PNP ligand. Ir(PNP)(Cl)₃ was characterized by x-ray crystallog.

Dalton Transactions 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, Application In Synthesis of 338800-13-8.

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

Gu, Shunyan published the artcileUse of Ligand Steric Properties to Control the Thermodynamics and Kinetics of Oxidative Addition and Reductive Elimination with Pincer-Ligated Rh Complexes, Safety of 2,6-Bis((di-tert-butylphosphino)methyl)pyridine, the publication is Organometallics (2020), 39(10), 1917-1933, database is CAplus.

Oxidative addition and reductive elimination reactions are central steps in many catalytic processes, and controlling the energetics of reaction intermediates is key to enabling efficient catalysis. Oxidative addition and reductive elimination reactions using (^RPNP)RhX complexes (R = tert-Bu, iso-Pr, mesityl and phenyl; X = Cl, I) were studied to deduce the impact of the size of the phosphine substituents. Using (^RPNP)RhCl as starting material, oxidative addition of MeI was observed to produce (^RPNP)Rh(Me)(I)Cl, which was followed by reductive elimination of MeCl to form (^RPNP)RhI. The thermodn. and kinetics vary with the identity of the substituent R” on P of the PNP ligand. The presence of large steric bulk (e.g., R = tert-Bu, mesityl) on the phosphine favors Rh(I) compared to the presence of two smaller substituents (e.g., R = iso-Pr, phenyl). An Eyring plot for the oxidative addition of MeI to (^tBuPNP)RhCl in THF-d₈ is consistent with a polar two-step reaction pathway, and the formation of [(^tBuPNP)Rh(Me)I]I is also consistent with this mechanism. DFT calculations show steric bulk affects the reaction energies of addition reactions that generate six-coordinate complexes by tens of kcal·mol^-1. Ligand steric bulk has a reduced effect (a few kcal·mol^-1) on S_N2 addition barriers, which only require access to one side of the square plane.

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, Safety of 2,6-Bis((di-tert-butylphosphino)methyl)pyridine.

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

Vogt, Matthias published the artcileActivation of Nitriles by Metal Ligand Cooperation. Reversible Formation of Ketimido- and Enamido-Rhenium PNP Pincer Complexes and Relevance to Catalytic Design, HPLC of Formula: 338800-13-8, the publication is Journal of the American Chemical Society (2013), 135(45), 17004-17018, database is CAplus and MEDLINE.

The dearomatized complex cis-[Re-(PNP^tBu*)-(CO)₂] (4) undergoes cooperative activation of CN triple bonds of nitriles via [1,3]-addition Reversible C-C and Re-N bond formation in 4 was investigated in a combined exptl. and computational study. The reversible formation of the ketimido complexes (5-7) was observed When nitriles bearing an alpha methylene group are used, reversible formation of the enamido complexes (8 and 9) takes place. The reversibility of the activation of the nitriles in the resulting ketimido compounds was demonstrated by the displacement of p-CF₃-benzonitrile from cis-[Re-(PNP^tBu-N=CPh^pCF3)-(CO)₂] (6) upon addition of an excess of benzonitrile and by the temperature-dependent [1,3]-addition of pivalonitrile to complex 4. The reversible binding of the nitrile in the enamido compound cis-[Re-(PNP^tBu-HNC=CHPh)-(CO)₂] (9) was demonstrated via the displacement of benzyl cyanide from 9 by CO. Computational studies suggest a stepwise activation of the nitriles by 4, with remarkably low activation barriers, involving precoordination of the nitrile group to the Re-(I) center. The enamido complex 9 reacts via β-carbon methylation to give the primary imino complex cis-[Re-(PNP^tBu-HN=CC-(Me)-Ph)-(CO)₂]-OTf 11. Upon deprotonation of 11 and subsequent addition of benzyl cyanide, complex 9 is regenerated and the monomethylation product 2-phenylpropanenitrile is released. Complexes 4 and 9 were found to catalyze the Michael addition of benzyl cyanide derivatives to α,β-unsaturated esters and carbonyls.

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 C14H12N2S, HPLC of Formula: 338800-13-8.

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

Mukherjee, Arup published the artcileManganese-Catalyzed Environmentally Benign Dehydrogenative Coupling of Alcohols and Amines to Form Aldimines and H₂: A Catalytic and Mechanistic Study, Related Products of pyridine-derivatives, the publication is Journal of the American Chemical Society (2016), 138(13), 4298-4301, database is CAplus and MEDLINE.

The catalytic dehydrogenative coupling of alcs. and amines to form aldimines represents an environmentally benign methodol. in organic chem. This has been accomplished in recent years mainly with precious-metal-based catalysts. We present the dehydrogenative coupling of alcs. and amines to form imines and H₂ that is catalyzed, for the first time, by a complex of the earth-abundant Mn. Detailed mechanistic study was carried out with the aid of NMR spectroscopy, intermediate isolation, and X-ray anal.

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, Related Products of pyridine-derivatives.

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

Semproni, Scott P. published the artcileFour-Coordinate Cobalt Pincer Complexes: Electronic Structure Studies and Ligand Modification by Homolytic and Heterolytic Pathways, Quality Control of 338800-13-8, the publication is Journal of the American Chemical Society (2014), 136(25), 9211-9224, database is CAplus and MEDLINE.

A family of cobalt chloride, Me, acetylide and hydride complexes bearing both intact and modified tert-Bu substituted bis(phosphino)pyridine pincer ligands has been synthesized and structurally characterized and their electronic structures evaluated. Treatment of the unmodified compounds with the stable nitroxyl radical, TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxidanyl) resulted in immediate H- atom abstraction from the benzylic position of the chelate yielding the corresponding modified pincer complexes, (^tBumPNP)CoX (X = H, CH₃, Cl, CCPh). Thermolysis of the Me and hydride derivatives, (^tBuPNP)CoCH₃ and (^tBuPNP)CoH, at 110° also resulted in pincer modification by H atom loss while the chloride and acetylide derivatives proved inert. The relative ordering of benzylic C-H bond strengths was corroborated by H atom exchange experiments between appropriate intact and modified pincer complexes. The electronic structures of the modified compounds, (^tBumPNP)CoX were established by EPR spectroscopy and DFT computations and are best described as low spin Co(II) complexes with no evidence for ligand centered radicals. The electronic structures of the intact complexes, (^tBuPNP)CoX were studied computationally and bond dissociation free energies of the benzylic C-H bonds were correlated to the identity of the X-type ligand on cobalt where pure σ donors such as hydride and Me produce the weakest C-H bonds. Comparison to a rhodium congener highlights the impact of the energetically accessible one-electron redox couple of the first row metal ion in generating weak C-H bonds in remote positions of the supporting pincer ligand.

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 0, Quality Control of 338800-13-8.

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

Arashiba, Kazuya published the artcileA molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia, Application In Synthesis of 338800-13-8, the publication is Nature Chemistry (2011), 3(2), 120-125, database is CAplus and MEDLINE.

The synthesis of transition metal-dinitrogen complexes and the stoichiometric transformation of their coordinated dinitrogen into ammonia and hydrazine have been the subject of considerable research, with a view to achieving nitrogen fixation under ambient conditions. Since a single example in 2003, no examples have been reported of the catalytic conversion of dinitrogen into ammonia under ambient conditions. The dimolybdenum-dinitrogen complex bearing PNP pincer ligands was found to work as an effective catalyst for the formation of ammonia from dinitrogen, with 23 equivalent of ammonia being produced with the catalyst (12 equivalent of ammonia are produced based on the molybdenum atom of the catalyst). This is another successful example of the catalytic and direct conversion of dinitrogen into ammonia under ambient reaction conditions. We believe that the results described in this Article provide valuable information with which to develop a more effective nitrogen-fixation system under mild reaction conditions.

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

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