2031-95-0

Usage

InChI:InChI=1/C2H6/c1-2/h1-2H3/i1D3

Upstream product

• 34557-54-5 methane 
• 558-20-3 methane 
• 666-52-4 [⁽²⁾H₆]acetone 
• 67-64-1 acetone 
• 74-84-0 ethane radical cation 
• 865-50-9 iodomethane-d3 
• 71-55-6 1,1,1-trichloroethane 
• 1396816-85-5 [(κ³-N,N'-dimethyl-2,11-diaza[3,3](2,6)pyridinophane)Pd^IV(CD₃)(CH₃)₂]I 

Downstream Products

• 34557-54-5 methane 
• 676-49-3 Monodeuteromethan 
• 74-84-0 ethane 

Relevant academic research and scientific papers

Changes in ligand coordination mode induce bimetallic C-C coupling pathways

Carbon-carbon coupling is one of the most powerful tools in the organic synthesis arsenal. Known methodologies primarily exploit monometallic Pd0/PdII catalytic mechanisms to give new C-C bonds. Bimetallic C-C coupling mechanisms that involve a PdI/PdII redox cycle, remain underexplored. Thus, a detailed mechnaistic understanding is imperative for the development of new bimetallic catalysts. Previously, a PdII-Me dimer (1) supported by L1, which has phosphine and 1-azaallyl donor groups, underwent reductive elimination to give ethane, a PdI dimer, a PdII monometallic complex, and Pd black. Herein, a comprehensive experimental and computational study of the reactivity of 1 is presented, which reveals that the versatile coordination chemistry of L1 promotes bimetallic C-C bond formation. The phosphine 1-azaallyl ligand adopts various bridging modes to maintain the bimetallic structure throughout the C-C bond forming mechanism, which involves intramolecular methyl transfer and 1,1-reductive elimination from one of the palladium atoms. The minor byproduct, methane, likely forms through a monometallic intermediate that is sensitive to solvent C-H activation. Overall, the capacity of L1 to adopt different coordination modes promotes the bimetallic C-C coupling channel through pathways that are unattainable with statically-coordinated ligands.

Properties and Reactivities of Zwitterionic Platinum(II)-ate Complexes Generated by Transforming Coordination of an Alkyne-Bisphosphine Ligand

Coordination of an alkyne-bisphosphine ligand with platinum(II) precursors produced a structural reorganization in the ligand backbone to form stable zwitterionic platinum(II) complexes bearing an anionic platinum center. The structural properties and reactivities of these complexes were investigated using X-ray crystallographic analyses, computational studies, and stoichiometric reactions involving oxidative addition and reductive elimination. These studies have shown that the enhanced nucleophilicity of the platinum center to alkyl halides promotes smooth oxidative addition and that the charge rebalance accelerates the dissociation of the halide anion from the platinum(IV) intermediate, which is essential in the carbon-carbon bond-forming step.

Axial Donor Effects on Oxidatively Induced Ethane Formation from Nickel-Dimethyl Complexes

Tetradentate pyridinophane ligands have been shown to stabilize uncommon high-valent palladium and nickel organometallic complexes. Described herein are the synthesis and detailed characterization of a series of NiII- and NiIII-dimethyl complexes supported by modified tetradentate pyridinophane ligands in which one or both of the N-methyl substituents were replaced with electron-withdrawing p-toluenesulfonyl groups, thus reducing the amine N atom donicity and favoring the formation of Ni complexes with lower coordination numbers. The corresponding NiII-dimethyl complexes exhibit accessible oxidation potentials, and their oxidation generates NiIII species that were characterized by EPR and X-ray crystallography. Moreover, the NiII-dimethyl complexes exhibit selective ethane formation upon oxidatively induced reductive elimination using various oxidants - including O2 and H2O2, without the generation of any C-heteroatom products. Overall, these results suggest that the (RN4)NiIIMe2 complexes with more weakly donating axial ligands are more reactive toward ethane formation, likely due to destabilization of the corresponding high-valent Ni intermediates and formation of 5- and 4-coordinate conformations for these Ni species.

Ligand-Induced Reductive Elimination of Ethane from Azopyridine Palladium Dimethyl Complexes

Reductive elimination (RE) is a critical step in many catalytic processes. The reductive elimination of unsaturated groups (aryl, vinyl and ethynyl) from Pd(II) species is considerably faster than RE of saturated alkyl groups. Pd(II) dimethyl complexes ligated by chelating diimine ligands are stable toward RE unless subjected to a thermal or redox stimulus. Herein, we report the spontaneous RE of ethane from (azpy)PdMe2 complexes and the unique role of the redox-active azopyridine (azpy) ligands in facilitating this reaction. The (azpy)PdMe2 complexes are air- and moisture-stable in the solid form, but they readily produce ethane upon dissolution in polar solvents at temperatures from 10 °C to room temperature without the need for an external oxidant or elevated temperatures. Experimental and computational studies indicate that a bimolecular methyl transfer precedes the reductive elimination step, where both steps are facilitated by the redox-active azopyridine ligand.

Isolated Organometallic Nickel(III) and Nickel(IV) Complexes Relevant to Carbon-Carbon Bond Formation Reactions

Nickel-catalyzed cross-coupling reactions are experiencing a dramatic resurgence in recent years given their ability to employ a wider range of electrophiles as well as promote stereospecific or stereoselective transformations. In contrast to the extensively studied Pd catalysts that generally employ diamagnetic intermediates, Ni systems can more easily access various oxidation states including odd-electron configurations. For example, organometallic NiIII intermediates with aryl and/or alkyl ligands are commonly proposed as the active intermediates in cross-coupling reactions. Herein, we report the first isolated NiIII-dialkyl complex and show that this species is involved in stoichiometric and catalytic C-C bond formation reactions. Interestingly, the rate of C-C bond formation from a NiIII center is enhanced in the presence of an oxidant, suggesting the involvement of transient NiIV species. Indeed, such a NiIV species was observed and characterized spectroscopically for a nickelacycle system. Overall, these studies suggest that both NiIII and NiIV species could play an important role in a range of Ni-catalyzed cross-coupling reactions, especially those involving alkyl substrates.

Bimetallic C-C Bond-Forming Reductive Elimination from Nickel

Ni-catalyzed cross-coupling reactions have found important applications in organic synthesis. The fundamental characterization of the key steps in cross-coupling reactions, including C-C bond-forming reductive elimination, represents a significant challenge. Bimolecular pathways were invoked in early proposals, but the experimental evidence was limited. We present the preparation of well-defined (pyridine-pyrrolyl)Ni monomethyl and monophenyl complexes that allow the direct observation of bimolecular reductive elimination to generate ethane and biphenyl, respectively. The sp3-sp3 and sp2-sp2 couplings proceed via two distinct pathways. Oxidants promote the fast formation of Ni(III) from (pyridine-pyrrolyl)Ni-methyl, which dimerizes to afford a bimetallic Ni(III) intermediate. Our data are most consistent with the subsequent methyl coupling from the bimetallic Ni(III) to generate ethane as the rate-determining step. In contrast, the formation of biphenyl is facilitated by the coordination of a bidentate donor ligand.

Metal ions do not play a direct role in the formation of carbon-carbon triple bonds during reduction of trihaloalkyls by CrII or V II

Carbyne radicals: Reactions of trihaloalkyl compounds with Cr2+ or V2+ in aqueous solutions yield alkynes and other products. Stepwise halogen abstractions from the trihaloalkyls form alkyl carbyne triradicals in solution. These radicals undergo coupling reactions, producing triply bonded alkyne molecules (see scheme). This process is not metal-assisted and does not occur in the coordination sphere of the metal ions.

Detection of Pd(III) and Pd(IV) intermediates during the aerobic oxidative C-C bond formation from a Pd(II) dimethyl complex

The dimethyl PdII complex (MeN4)Pd IIMe2 (MeN4 = N,N′-dimethyl-2,11-diaza[3, 3](2,6)pyridinophane) is readily oxidized by dioxygen in the presence of protic solvents to selectively eliminate ethane. UV-vis, EPR, ESI-MS, and NMR studies reveal the formation of several PdIII and PdIV intermediates during the aerobically induced C-C bond formation reaction, including the key intermediate [(κ3-MeN4)Pd IVMe3]+, which leads to ethane elimination. The latter complex was also synthesized independently and structurally characterized to reveal a distorted octahedral geometry that is proposed to promote facile reductive elimination. Overall, this study represents a rare example of aerobic oxidation of an organometallic PdII precursor that leads to a well-defined PdIV species, which undergoes selective C-C bond formation under ambient conditions.

Mechanistic considerations for C-C bond reductive coupling at a cobalt(III) center

The diamagnetic cobalt(III) dimethyl complex, cis,mer-(PMe 3)3Co(CH3)2I, was found to promote selective C-C bond formation, affording ethane and triplet (PMe 3)3CoI. The mechanism of reductive elimination has been investigated by a series of kinetic and isotopic-labeling experiments. Ethane formation proceeds with a rate constant of 3.1(5) × 10-5 s -1 (50 °C) and activation parameters of ΔH a = 31.4(8) kcal/mol and ΔS a = 17(3) eu. Addition of free trimethylphosphine or coordinating solvent strongly inhibits reductive elimination, indicating reversible phosphine dissociation prior to C-C bond-coupling. EXSY NMR analysis established a rate constant of 9(2) s-1 for phosphine loss from cis,mer-(PMe3)3Co(CH3)2I. Radical trapping, crossover, and isotope effect experiments were consistent with a proposed mechanism for ethane extrusion where formation of an unobserved five-coordinate intermediate is followed by concerted C-C bond formation. An unusual intermolecular exchange of cobalt-methyl ligands was also observed by isotopic labeling.

Isothermal pyrolysis of iodomethanes in gases

The fact was established that the pyrolysis of gaseous iodomethanes RI yields methane and non traces of recombination products R2. A pyrolysis mechanism was proposed and rate constants of limiting stages of the pyrolysis of iodomethane, trideuteroiodomethane, and diiodomethane over the range of 500-1500 K were determined. Pleiades Publishing, Ltd., 2009.