Category: 68569-14-2

Xing, Yang-Yang published the artcileA Computational Mechanistic Study of Pd(II)-Catalyzed Enantioselective C(sp³)-H Borylation: Roles of APAO Ligands, Computed Properties of 68569-14-2, the publication is Journal of Organic Chemistry (2019), 84(17), 10690-10700, database is CAplus and MEDLINE.

A computational mechanistic study has been performed on Pd(II)-catalyzed enantioselective reactions involving acetyl-protected aminomethyl oxazolines (APAO) ligands that significantly improved reactivity and selectivity in C(sp³)-H borylation. The results support a mechanism including initiation of C(sp³)-H bond activation generating a five-membered palladacycle and ligand exchange, followed by HPO₄^2--promoted transmetalation. These resulting Pd(II) complexes further undergo sequential reductive elimination by coordination of APAO ligands and protonation to afford the enantiomeric products and deliver Pd(0) complexes, which will then proceed by oxidation and deprotonation to regenerate the catalyst. The C(sp³)-H activation is found to be the rate- and enantioselectivity-determining step, in which the APAO ligand acts as the proton acceptor to form the two enantioselectivity models. The results demonstrate that the diverse APAO ligands control the enantioselectivity by differentiating the distortion and interaction between the major and minor pathways.

Journal of Organic Chemistry published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C7H7IN2O, Computed Properties of 68569-14-2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Giri, Ramesh published the artcileSynthetic Applications of Pd(II)-Catalyzed C-H Carboxylation and Mechanistic Insights: Expedient Routes to Anthranilic Acids, Oxazolinones, and Quinazolinones, HPLC of Formula: 68569-14-2, the publication is Journal of the American Chemical Society (2010), 132(2), 686-693, database is CAplus and MEDLINE.

A Pd(II)-catalyzed reaction protocol for the carboxylation of ortho-C-H bonds in anilides to form N-acyl anthranilic acids has been developed. This reaction procedure provides a novel and efficient strategy for the rapid assembly of biol. and pharmaceutically significant mols., such as benzoxazinones and quinazolinones, from simple anilides without installing and removing an external directing group. The reaction conditions are also amenable to the carboxylation of N-phenylpyrrolidinones. A monomeric palladacycle containing p-toluenesulfonate as an anionic ligand has been characterized by X-ray crystallog., and the crucial role of p-toluenesulfonic acid in the activation of C-H bonds in the presence of carbon monoxide is discussed. Identification of two key intermediates, a mixed anhydride and benzoxazinone formed by reductive elimination from organometallic Ar(CO)Pd(II)-OTs species, provides mechanistic evidence for a dual-reaction pathway.

Journal of the American Chemical Society published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, HPLC of Formula: 68569-14-2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Wendt, Ola F. published the artcileAcetonitrile and propionitrile exchange at palladium(II) and platinum(II), COA of Formula: C10H12F6N4O6PdS2, the publication is Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1997), 4733-4738, database is CAplus.

Ligand exchange at square-planar [Pd(MeCN)₄]²⁺ and [Pd(EtCN)₄]²⁺ has been studied by ¹H NMR line broadening and at [Pt(MeCN)₄]²⁺ and [Pt(EtCN)₄]²⁺ by isotopic labeling using ¹H NMR spectroscopy in deuterated nitromethane. Exchange takes place via two-term rate laws R_ex/4 = (k₁ + k₂[RCN])c_M with well defined k₁ paths. Rate constants per co-ordination site k₁²⁹⁸/s^-1, k₂²⁹⁸/kg mol^-1 s^-1 are 6.9 ± 1.6, 34 ± 3; 0.59 ± 0.12, 34 ± 3; 10.7 ± 1.8, 35 ± 4; (5.1 ± 2.3) × 10^-6, (2.8 ± 0.2) × 10^-5 and (5.5 ± 1.0) × 10^-6, (3.3 ± 0.2) × 10^-5 for [Pd(MeCN)₄][CF₃SO₃]₂, [Pd(MeCN)₄][BF₄]₂, [Pd(EtCN)₄][CF₃SO₃]₂, [Pt(MeCN)₄][CF₃SO₃]₂ and [Pt(EtCN)₄][CF₃SO₃]₂, resp. For [Pd(MeCN)₄]²⁺ the k₁ path is much larger for triflate than for tetrafluoroborate as counter ion. Changing the tetrafluoroborate concentration has no effect on the exchange rate of acetonitrile at [Pd(MeCN)₄]²⁺. In this case the k₁ path is ascribed to an attack by solvent at the metal center. For triflate saturation kinetics is observed This can be rationalized in terms of ion-pair formation followed by reversible intramol. exchange of nitrile for triflate within the ion pair, with an equilibrium constant K_ip³⁰⁰ = 8 ± 2 kg mol-¹ and a rate constant k³⁰⁰ = 12.5 ± 1.3 s^-1. All activation entropies are neg., indicating associative activation. A new, simple one-step synthesis of the substrate complexes as their triflate salts, using [M(acac)₂] (acac = acetylacetonate) as starting material, and of [Pd(MeCN)₄][BF₄]₂ using palladium(II) acetate, is described.

Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C25H29N9O3, COA of Formula: C10H12F6N4O6PdS2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Tiburcio, Jorge published the artcileConformational Behavior and Coordination Chemistry of 2,11-Dithia[3.3]orthocyclophane with Platinum Group Metals, Synthetic Route of 68569-14-2, the publication is Inorganic Chemistry (2002), 41(14), 3779-3785, database is CAplus and MEDLINE.

The compound 2,11-dithia[3.3]orthocyclophane (L) is a mesocyclic dithioether that can act as a bidentate ligand in different conformations. In the ionic heteroleptic complexes [PtL(η⁴-cod)][CF₃SO₃]₂ (1), [RhL(η⁴-cod)][CF₃SO₃] (2), and [IrL(η⁴-cod)][CF₃SO₃] (3) (cod = 1,5-cyclooctadiene), L is coordinated in the anti I conformation both in solution and in the solid state, as revealed by an x-ray diffraction study of complex 1. However, in [PdL(PPh₃)₂][SO₃CF₃]₂ (4) and [PtL(PPh₃)₂][SO₃CF₃]₂ (5), L exhibits two different conformations:anti I and anti II in a 40:60 ratio, as observed by ¹H and ³¹P NMR spectroscopy, with no exchange up to 90°. The homoleptic complexes [PdL₂][SO₃CF₃]₂ (6) and [PtL₂][SO₃CF₃]₂ (7), with two ligands bound to the metal, display two isomers in solution, one of them with L in conformations anti I-anti II and the other with conformations anti II-anti II with a 75:25 ratio. The x-ray structure of 6 showed only the presence of the anti II-anti II isomer in the solid state. All complexes were synthesized by the reaction of a suitable chloride complex with 2 equiv of Ag triflate and 1 equiv of L.

Inorganic Chemistry published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C23H43NP2, Synthetic Route of 68569-14-2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Chen, Chaohuang published the artcilePalladium(II)-Catalyzed Aminotrifluoromethoxylation of Alkenes: Mechanistic Insight into the Effect of N-Protecting Groups, Category: nitriles-buliding-blocks, the publication is Chinese Journal of Chemistry (2020), 38(4), 346-350, database is CAplus.

An efficient palladium-catalyzed regioselective 5-exo aminotrifluoromethoxylation of alkenes was established herein, which provided a practical route toward the synthesis of OCF₃-containing pyrrolidines such as I [R¹ = H, allyl, 4-ClC₆H₄, etc.; R² = allyl, Bn, 4-FC₆H₄, etc.; R¹R² = (CH₂)₃, (CH₂)₄, (CH₂)₂O(CH₂)₂, etc.] and II. Tert-Butyloxycarbonyl (Boc) as an amino protecting group played a significant role in both chemo- and regioselectivities. In addition, preliminary mechanistic studies revealed that amino protecting group of substrates and counter anion of palladium catalyst play critical roles in reaction efficiency presumably due to an isomerization of alkyl- Pd(II) intermediates. Moreover, the asym. 5-exo aminotrifluoromethoxylation reaction had also been achieved by introducing a sterically bulky pyridinyl-oxazoline ligand.

Chinese Journal of Chemistry published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Category: nitriles-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Huang, Deguang published the artcileReactions of the Terminal Ni^II-OH Group in Substitution and Electrophilic Reactions with Carbon Dioxide and Other Substrates: Structural Definition of Binding Modes in an Intramolecular Ni^II···Fe^II Bridged Site, Application In Synthesis of 68569-14-2, the publication is Journal of the American Chemical Society (2010), 132(13), 4693-4701, database is CAplus and MEDLINE.

A singular feature of the catalytic C-cluster of CO dehydrogenase is a sulfide-bridged Ni···Fe locus where substrate is bound and transformed in the reversible reaction CO + H₂O â‡?CO₂ + 2H⁺ + 2e^–. A similar structure was sought. Mononuclear planar Ni^II complexes [Ni(pyN₂^Me2)L]^1- (pyN₂^Me2 = bis(2,6-dimethylphenyl)-2,6-pyridinedicarboxamidate(2-)) derived from a NNN pincer ligand were prepared including L = OH^– (1) and CN^– (7). Complex 1 reacts with Et formate and CO₂ to form unidentate L = HCO₂^– (5) and HCO₃^– (6) products. A binucleating macrocycle was prepared which specifically binds Ni^II at a NNN pincer site and five-coordinate Fe^II at a triamine site. The Ni^II macrocycle forms [Ni(OH)(pyN₂dien^Me3)L]^1- (14) and [Ni(CN)(pyN₂dien^Me3)L]^1-complexes (15) analogous to 1 and 7. Reaction of 14 with FeCl₂ alone and with Et formate and 15 with FeCl₂ affords mols. with the Ni^II-L-Fe^II bridge unit in [Ni(L)FeCl(⊂pyN₂dien^Me3)]^1- (⊂pyN₂dien^Me3 = I) in which L = μ₂:η¹-OH^– (17) and μ₂:η²-HCO₂^– (18) and -CN^– (19). All bridges are nonlinear (17, 140.0°; 18, M-O-C 135.9° (Ni), 120.2° (Fe); 19, Ni-C-N 170.3°, Fe-N-C 141.8°) with Ni···Fe separations of 3.7-4.8 Å. The Ni^IIFe^II complexes, lacking appropriate Ni-Fe-S cluster structures, are not site analogs, but their synthesis and reactivity provide the 1st demonstration that mol. Ni^II···Fe^II sites and bridges can be attained, a necessity in the biomimetic chem. of C-clusters.

Journal of the American Chemical Society published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Application In Synthesis of 68569-14-2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Haselwander, T. F. A. published the artcileVinylic polymerization of norbornene by Pd(II) catalysis in the presence of ethylene, Product Details of C10H12F6N4O6PdS2, the publication is Macromolecular Rapid Communications (1997), 18(8), 689-697, database is CAplus.

Pd(II) catalysts with nitrilo ligands and BF₄^– counter ions give the best results in vinylic polymerization of norbornene. Absolute mol. weight determination of polynorbornene (PN) by means of light scattering and the 3-dimensional shape of PN were also investigated. Correlation of mol. weights M̅_w with intrinsic viscosity (Staudinger-index) [η] gave a close to 0.5 exponent for the Mark-Houwink equation with solvents chlorobenzene and cyclohexane at 25° as expected for polymer mols. with confined conformation. The vinylic polymerization of norbornene with [(CH₃CN)₄Pd][BF₄]₂ in nitromethane in the presence of ethylene results in PN with narrow mol. weight distribution. No termination and transfer reactions were found, nor any incorporation of ethylene could be detected.

Macromolecular Rapid Communications published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Product Details of C10H12F6N4O6PdS2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Gramage-Doria, Rafael published the artcileGold(I) Catalysis at Extreme Concentrations Inside Self-Assembled Nanospheres, Related Products of nitriles-buliding-blocks, the publication is Angewandte Chemie, International Edition (2014), 53(49), 13380-13384, database is CAplus and MEDLINE.

Homogeneous transition-metal catalysis is a crucial technol. for the sustainable preparation of valuable chems. The catalyst concentration is usually kept as low as possible, typically at mM or μM levels, and the effect of high catalyst concentration is hardly exploited because of solubility issues and the inherent unfavorable catalyst/substrate ratio. Herein, a self-assembly strategy is reported which leads to local catalyst concentrations ranging from 0.05 M to 1.1 M, inside well-defined nanospheres, while the overall catalyst concentration in solution remains at the conventional mM levels. The authors disclose that only at this high concentration, the gold(I) chloride is reactive and shows high selectivity in intramol. C-O and C-C bond-forming cyclization reactions.

Angewandte Chemie, International Edition published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Related Products of nitriles-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Clauss, Reike published the artcilePhosphorus guiding palladium: [4 + 4] metallomacrocyclic Pd^II complex and self-assembly of heterometallic Pd^II/Zn^II grid-type complex, Related Products of nitriles-buliding-blocks, the publication is Dalton Transactions (2022), 51(25), 9632-9641, database is CAplus and MEDLINE.

The reaction of heteroditopic ligand 1 featuring a hard pyridine-hydrazone-pyrimidine (N,N,N) site and a softer pyrimidine-hydrazone-phosphane (N,N,P) pocket with [Pd(CH₃CN)₄](OTf)₂ in different metal-to-ligand ratios (M:L) gave the homobimetallic Pd^II complex [Pd₂(1)(CH₃CN)₂](OTf)₄ (2, M:L ratio 2:1), the [4 + 4] metallomacrocyclic Pd^II complex [Pd(1)]₄(OTf)₈ (3, M:L ratio 1:1) and the monometallic complex [Pd(1)₂](OTf)₂ (4, M:L ratio 1:2). The soft N,N,P pocket preferably coordinates Pd^II, while the harder N,N,N coordination site selectively binds Zn^II forming the homoleptic meridional “corner” complexes [Zn(1)₂](OTf)₂ (5) and [Pd₂Zn(1)₂](OTf)₆ (6). The distinctive coordination behavior of ligand 1 is highlighted by the self-assembly of the heterometallic Pd^II/Zn^II grid-type complex [Pd₂Zn₂(1)₂](OTf)₈ (7) in a one-pot reaction. Complexes 2–7 were characterized by mass spectrometry, UV/Vis and NMR spectroscopy including DOSY NMR, and single-crystal X-ray diffraction studies were performed for 2–4 and 7.

Dalton Transactions published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Related Products of nitriles-buliding-blocks.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts

Chen, Zhi-Min published the artcilePalladium-Catalyzed Enantioselective Redox-Relay Heck Arylation of 1,1-Disubstituted Homoallylic Alcohols, Computed Properties of 68569-14-2, the publication is Journal of the American Chemical Society (2016), 138(36), 11461-11464, database is CAplus and MEDLINE.

An enantioselective redox-relay oxidative Heck arylation of 1,1-disubstituted alkenes to construct β-stereocenters was developed using a new pyridyl-oxazoline ligand. Various 1,2-diaryl carbonyl compounds were readily obtained in moderate yield and good to excellent enantioselectivity. Addnl., anal. of the reaction outcomes using multidimensional correlations revealed that enantioselectivity is tied to specific electronic features of the 1,1-disubstituted alkenol and the extent of polarizability of the ligand.

Journal of the American Chemical Society published new progress about 68569-14-2. 68569-14-2 belongs to nitriles-buliding-blocks, auxiliary class Palladium, name is Tetrakis(acetonitrile)palladium(II) Ditriflate, and the molecular formula is C10H12F6N4O6PdS2, Computed Properties of 68569-14-2.

Referemce:
https://en.wikipedia.org/wiki/Nitrile,
Nitriles – Chemistry LibreTexts