A novel [Mg2(μ-Cl)2](2+) cation complex, which is highly active for reversible Mg electrodeposition, was identified the first time in this work. This complex found to be present electrolytes formulated dimethoxyethane (DME) through dehalodimerization of non-nucleophilic MgCl2 by reacting with either salts (such as Mg(TFSI)2, TFSI = bis(trifluoromethane)sulfonylimide) or Lewis acid AlEtCl2 AlCl3). The molecular structure characterized single crystal X-ray diffraction, Raman spectroscopy and...

The reaction of Ni(COD)(2), IPr, and nitrile affords dimeric [Ni(IPr)RCN](2) in high yields. X-ray analysis revealed these species display simultaneous η(1)- η(2)-nitrile binding modes. These dimers are catalytically competent the formation pyridines from cycloaddition diynes nitriles. Kinetic showed to be first order [Ni(IPr)RCN](2), zeroth added nitrile, diyne. Extensive stoichiometric competition studies were performed, selective incorporation exogenous, not dimer bound, was observed....

Abstract A variety of bicyclic N , ‐disubstituted 2‐aminopyridines have been prepared from diynes and cyanamides by nickel‐catalyzed [2+2+2] cycloaddition reactions. The reactions proceeded at room temperature with low catalyst loading to afford in good excellent yields. method is amenable both internal terminal proceeds a regioselective manner. number diverse functional group tolerance were used. intermolecular version employing 3‐hexyne ‐cyanopyrrolidine also afforded the desired...

A detailed mechanistic evaluation of the Ni(IPr)2-catalyzed [2 + 2 2] cycloaddition diynes and nitriles was conducted. Through kinetic analysis these reactions, observed regioselectivities products, stoichiometric cycloadditions appear to proceed by a heterooxidative coupling mechanism, in contrast other common catalysts. Reaction profiles demonstrated strong dependence on nitrile, resulting variable nitrile-dependent resting states. The coordination considerable steric bulk carbene ligands...

A comprehensive study of the reactions chelating phosphines with Ni(cod)2 to form (phosphine)Ni(cod), (phosphine)2Ni, or mixtures thereof is presented. series (phosphine)Ni(cod) complexes were isolated and characterized. The structural differences between (phosphine)2Ni examined using X-ray crystallography 1H 31P NMR spectroscopy. In addition, effects ring size, rigidity, bulk phosphine backbone on formation either investigated. These studies show that Ni–P bond lengths in both size formed...

A general synthetic route to the first Xantphos nickel alkyne and alkene complexes has been discovered.

Abstract Spin waves, quantized as magnons, have low energy loss and magnetic damping, which are critical for devices based on spin‐wave propagation needed information processing devices. The organic‐based magnet [V(TCNE) x ; TCNE = tetracyanoethylene; ≈ 2] has shown an extremely damping comparable to, example, yttrium iron garnet (YIG). excitation, detection, utilization of coherent non‐coherent spin waves various modes in V(TCNE) is demonstrated show that the angular momentum carried by...

The investigation of the stereoelectronic influence N-aryl substituted NHC ligands on Ni(0) is reported. structural analysis a family [(NHC)Ni(styrene)2] complexes are correlated to known literature parameters (TEP and %VBur). involved NMR spectroscopic techniques X-ray crystallography isolated complexes. synthesis characterization this user-friendly easy accessible precatalysts can be realized in two-step starting from deprotonation imidazolium salt followed by direct coordination onto...

The cross-coupling of alkyl cyanamides with a number aryl, heteroaryl, and vinyl halide pseudohalide coupling partners has been developed via modification Pd-catalyzed amidation methods. reactions proceed selectively under mild conditions reasonable reaction times in moderate to excellent yields.

We report solvent and electrolyte effects on the electrocatalytic oxidation of H2 using Ni(P(Cy)2N(R')2)2 (R = Bn, (t)Bu) complexes. A turnover frequency 46 s(-1) for Ni(P(Cy)2N(Bn)2)2 was obtained 0.2 M [(n)Bu4N][BF4] in THF. 51 observed Ni(P(Cy)2N(tBu)2)2 [(n)Bu4N][B(C6F5)4] fluorobenzene. These observations, conjunction with previous studies, indicate nitrile binding inhibits catalysis supported by Ni(P(Cy)2N(Bn)2)2.

The regioselectivity of the Ni/SIPr-catalyzed cycloaddition terminal alkynes and cyanamides was explored. In general, 3,5-disubstituted 2-aminopyridines were formed as major product.

Abstract Organic‐based magnetic materials have been used for spintronic device applications as electrodes of spin aligned carriers and spin‐pumping substrates. Their advantages over more traditional inorganic magnets include reduced damping lower fabrication costs. Vanadium tetracyanoethylene, V[TCNE] x ( ≈ 2), is an organic‐based ferrimagnet with above room‐temperature order temperature T c 400 K). has deposition flexibility can be grown on a variety substrates via low‐temperature chemical...

Abstract The synthesis of the 1,5‐diphenyl‐3,7‐diisopropyl‐1,5‐diaza‐3,7‐diphosphacyclooctane ligand, P i Pr 2 N Ph , is reported. Two equivalents ligand react with [Ni(CH 3 CN) 6 ](BF 4 ) to form bis(diphosphine)–Ni II complex [Ni(P which acts as a proton reduction electrocatalyst. In addition ] 2+ we report and structural characterization Ni 0 Ni(P –hydride [HNi(P ]BF . represents first in R R′ family compounds be structurally characterized. experimental data, mechanism electrocatalysis...

Electronically variant (dppf)Ni(ketene) complexes were synthesized and characterized to perform kinetic analysis on their decomposition through a decarbonylation/disproportion process Ni–CO alkenes. Ligands containing electron-donating groups stabilized such complexes, whereas an electron-withdrawing group was found destabilize them. Hammett the reaction revealed buildup of negative charges in rate-determining step, which corroborates past computational models.

Two new Ni(II) complexes, the homoleptic [Ni(8PCy2NH)2]2+ complex (8PCy2NH = 3,7-cyclohexyl-1-amino-3,7-diphosphacyclooctane) containing two pendant amines on adjacent ligands, and heteroleptic [Ni(8PCy2NH)(dppe)]2+ (dppe bis(diphenylphosphino)ethane) only a single amine, have been synthesized, their electrochemical properties are reported. The is capable of heterolytically cleaving hydrogen, allowing for first observation an endo-protonated nickel hydride related to [Ni(PR2NR′2)2]2+ family...

A mechanistic investigation into the origins of regio- and chemoselectivities observed in iron/pyridine dialdimine (PDAI)-catalyzed intermolecular [2+2+2] cycloaddition reactions terminal alkynes cyanamides to yield substituted 2-amino-pyridines is reported. The combination experimental computational studies disclosed herein reveals role hemilabile PDAI ligand as an important factor controlling resultant product's chemoselectivity.

A Ni-catalyzed (4 + 2) cycloaddition of alkynes and azetidinones toward piperidinones was used as key reaction in the enantioselective synthesis naturally occurring indolizidine alkaloids. The benefits from use an easily accessible azetidinone advanced divergent intermediate to build core. This methodology has been applied total syntheses (+)-septicine, (+)-ipalbidine, (+)-seco-antofine illustrate applicability general approach.

This study revisits the electroabsorption (EA) spectrum of polyacetylene, as functions electric field strength, isomerization degree, and light polarization states. The EA $cis$-$(CH)_x$ reveals an oscillatory feature that follows Stark shift-related first derivative materials absorption contains v(0-1) v(0-2) sidebands excited $C=C$ stretching vibration agrees well with Raman spectrum. $trans $-$(CH)_x$ does not match spectrum, phonon sideband frequency agree RS a band below allowed $1B_u$...

This study revisits the electroabsorption (EA) spectrum of polyacetylene, ${(\mathrm{CH})}_{\mathrm{x}}$ thin films, for both cis- and trans-isomers, as functions electric field strength, isomerization degree, light polarization states. The EA cis-${(\mathrm{CH})}_{\mathrm{x}}$ reveals an oscillatory feature that follows Stark shift-related first derivative material's absorption contains $v$(0-1) $v$(0-2) sidebands excited $\mathrm{C}=\mathrm{C}$ stretching vibration agrees well with Raman...

The synthesis and spectroscopic data of six Group 6 metal complexes with the silylphosphine ligands, P(C6 H5 ){Si(CH3 )3 }2 P(H){Si(CH3 are reported. crystal structures M(P{R}{TMS}2 )(CO)5 , M = Cr, Mo, W; R C6 Cr; H