112724-99-9

Upstream product

• 924896-53-7 Rh(P(Cyp)2(η2-C5H7))(η6-(C6H3(CF3)2)B(C6H3-3,5-(CF3)2)3) 
• 1643-19-2 tetrabutylammomium bromide 
• 160298-76-0 silver(I) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate 
• 429-41-4 tetrabutyl ammonium fluoride 
• 3109-63-5 tert-butylammonium hexafluorophosphate(V) 
• 79060-88-1 sodium tetrakis[(3,5-di-trifluoromethyl)phenyl]borate 

Relevant academic research and scientific papers

Reductive Carbonylation of [NiCl2(dippf)] (dippf = 1,1′-Bis(diisopropylphosphino)ferrocene) with Fe(CO)5 and (Spectro)electrochemistry of the Resulting [Ni(CO)2(dippf)]

[Ni(CO)2(dippf)] [1] (dippf = 1,1′-bis(diisopropylphosphino)ferrocene) was synthesized from [NiCl2(dippf)] and [Fe(CO)5] at elevated temperature/pressure using microwave (MW) heating. [1] showed two oxidation waves in the cyclic voltammogram, and UV-vis-NIR spectroelectrochemistry (SEC) and IR SEC at -30 °C as well as computation support by means of DFT were used to determine the location and electron configuration after both oxidation events. The monocation [1]+ showed a strong NIR absorption in the UV-vis-NIR spectrum that was a IVCT [NiI → FeII] and inverse IVCT (iIVCT) [FeII → NiI], and the IR SEC spectrum of [1]+ showed multiple bands associated with two similar configurations, one where the spin is delocalized over both metal atoms and a second configuration where the spin is Ni localized. The second oxidation to [1]2+ occurred at the Ni atom and resulted in the formation of a Fe → Ni dative bond.

Effect of Large Electrolyte Anions on the Sequential Oxidations of Bis(fulvalene)diiron Attached to Glassy Carbon by an Ethynyl Linkage

Two ethynyl-derivatized isomers of bis(fulvalene)diiron (BFD, 1,1′-biferrocenylene) were prepared and covalently attached to glassy carbon electrodes through their ethynyl group by three different electrode modification methods. Cyclic voltammetry and square wave (SW) voltammetry were used to characterize surface coverages of 1.4-5.5 × 10-10 mol cm-2, the higher of these corresponding to roughly a monolayer, based on computation of an idealized close-packing structure for ethynylbis(fulvalene)diiron (E-BFD) on a solid surface. In a dichloromethane solution containing a smaller electrolyte anion such as [PF6]- or [ClO4]-, the E-BFD-modified electrodes exhibited two quasi-Nernstian one-electron oxidations. In contrast, the current for the second oxidation process, [E-BFD]+/2+, was diminished in electrolytes containing one of the large fluoroaryl borate anions, [B(C6F5)4]- or [B(C6H3(CF3)2)4]-. The effect was enhanced for electrodes having higher surface coverages being probed at shorter voltammetric time scales. SW voltammetry showed that the diminished currents for [E-BFD]+/2+ in large-anion electrolytes are not caused by slow electron transfer. Rather, they are attributed to mixed diffusivity of the counter-anions at the electrode/solution interface, as [E-BFD]+ and the anion form the optimum (lowest-energy) configuration of a 1:1 ion pair. The interior transport of the anion required to reach this configuration may be sterically encumbered, accounting for the diminished charge transfer observed with electrolytes containing large anions.

Effects of Charged Ligand Substituents on the Properties of the Formally Copper(III)-Hydroxide ([CuOH]2+) Unit

With the goal of understanding how distal charge influences the properties and hydrogen atom transfer (HAT) reactivity of the [CuOH]2+ core proposed to be important in oxidation catalysis, the complexes [M]3[SO3LCuOH] (M = [K(18-crown-6)]+ or [K(crypt-222)]+) and [NMe3LCuOH]X (X = BArF4- or ClO4-) were prepared, in which SO3- or NMe3+ substituents occupy the para positions of the flanking aryl rings of the supporting bis(carboxamide)pyridine ligands. Structural and spectroscopic characterization showed that the [CuOH]+ cores in the corresponding complexes were similar, but cyclic voltammetry revealed the E1/2 value for the [CuOH]2+/[CuOH]+ couple to be nearly 0.3 V more oxidizing for the [NMe3LCuOH]2+ than the [SO3LCuOH]- species, with the latter influenced by interactions between the distal -SO3- substituents and K+ or Na+ counterions. Chemical oxidations of the complexes generated the corresponding [CuOH]2+ species as evinced by UV-vis spectroscopy. The rates of HAT reactions of these species with 9,10-dihydroanthracene to yield the corresponding [Cu(OH2)]2+ complexes and anthracene were measured, and the thermodynamics of the processes were evaluated via determination of the bond dissociation enthalpies (BDEs) of the product O-H bonds. The HAT rate for [SO3LCuOH]- was found to be 150 times faster than that for [NMe3LCuOH]2+, despite finding approximately the same BDEs for the product O-H bonds. Rationales for these observations and new insights into the roles of supporting ligand attributes on the properties of the [CuOH]2+ unit are presented.

Charge generation in low-polarity solvents: Poly(ionic liquid)- functionalized particles

We present a straightforward strategy for the synthesis of highly charged poly(ionic liquid)-functionalized particles in low-polarity solvents. A series of cationic liquid monomers consisting of a tetraalkyl ammonium cation and a fluorinated tetrakis[phenyl] borate anion linked, via a C3-alkyl chain, to a methacrylate unit were synthesized. The addition of this ionic monomer to a conventional dispersion polymerization of methyl methacrylate and methacrylic acid at 80 C in a mixed dodecane/hexane solvent yielded spherical, highly monodisperse particles with mean diameters of between ～50 and 2500 nm with high electrophoretic mobility and stability in nonpolar solvents such as dodecane. The surface potential in dodecane could be adjusted in the range from 0 to 180 ± 9 mV by altering the ratio of ionic monomer to methacrylate monomers. The particles open up new opportunities for the electrostatic assembly of nanoparticles and organized structures in nonpolar environments.

Ion pairs of weakly coordinating cations and anions: Synthesis and application for sulfide to sulfoxide oxidations

A series of salts containing the weakly coordinating cations (WCC) 1-butyl-3-methylimidazolium ([Bmim]+), 1-butyl-2,3-dimethylimidazolium ([Bdmim]+), 1-dodecyl-3-methylimidazolium ([C12mim]+), tetrabutylphosphonium ([PBu4]+), tributyltetradecyl

Interaction between anions and molybdenum allyl dicarbonyl complexes of 1,4,7-trithiacyclononane

The labile complex [MoCl(η3-methallyl)(CO) 2(NCMe)2] reacts with the ligand 1,4,7-trithiacyclononane ([9]aneS3) and the salt NaBAr'4 to afford [Mo(η3-methallyl)(CO)2([9]aneS3)][BAr' 4] (1·BAr'4). An analogous reaction of [MoBr(η3-allyl)(CO)2(NCMe)2] yields [Mo(η3-allyl)(CO)2([9]aneS3)][BAr' 4] (2·BAr'4). The new compounds 1·BAr' 4 and 2·BAr'4 were characterized by IR and NMR spectroscopic analysis and X-ray diffraction studies. Both compounds feature the cyclic thioether [9]aneS3 coordinated as a tridentate ligand to the molybdenum center. The allyl ligand in 2·BAr'4 is aligned with the middle of the OC-Mo-CO angle, which is acute. Both of these features are typical of most pseudo-octahedral allyl dicarbonyl molybdenum complexes. In contrast, the allyl group is rotated in 1·BAr'4, which is attributed to steric hindrance between the methyl substituent and the ligated thioether, and the OC-Mo-CO angle is obtuse. Compound 1·BAr'4 undergoes rapid substitution of [9]aneS3 by either chloride and fluoride ions in dichloromethane, and the products include the known species [{Mo(η3-methallyl)(CO)2}2(μ-Cl) 3]- and a structurally similar new anionic complex with two fluoro and one hydroxo bridging ligands, respectively. Stable supramolecular adducts were formed in the reactions of 1·BAr'4 and 2·BAr4 with bromide, iodide, hydrogensulfate, and methanesulfonate compounds. The binding constants of these adducts in dichloromethane were calculated from 1H NMR spectroscopic titration data, and the solid-state structures of the 1·Br, 1·HSO 4, 1·I, and 2·I adducts were determined by X-ray diffraction studies. The surprising slightly higher stability of the iodide adduct relative to that of bromide was investigated theoretically, with the results pointing to an effect of the differential solvation of the halide ions.

Diferrocenyl molecular wires. the role of heteroatom linkers

Diferrocenyl molecular "wires", in which two ferrocenes are linked by a conjugated chain, allowing the communication of redox information between the ferrocenes, are a versatile platform on which to investigate notions of molecular conductivity. In this paper, we examine the role of heteroatoms=including O, P, S, and Se, as well as C atoms in various oxidation states=separated from the ferrocenes by intervening double bonds which minimize any steric effects. Surprisingly, oxygen is a better electronic mediator than sulfur, a phenomenon we attribute to superior molecular orbital overlap. These fundamental studies on redox coupling will help to guide the design of efficient organic conductors for organic electronics.

Synthesis, structure, spectroscopy and redox energetics of a series of uranium(IV) mixed-ligand metallocene complexes

A series of uranium(IV) mixed-ligand amide-halide/pseudohalide complexes (C5Me5)2U[N(SiMe3)2](X) (X = F (1), Cl (2), Br (3), I (4), N3 (5), NCO (6)), (C 5Me5)2/s

Rhodium phosphine olefin complexes of the weakly coordinating anions [BAr4F]- and [1-closo-CB11H 6Br6]-. Kinetic versus thermodynamic factors in anion coordination and complex reactivity

Solution and solid-state structures for the pair of complexes Rh{P(Cyp 2)(η2-C5H7)}{η6- (C6H3(CF3)2)BAr3 F} and Rh{P(Cyp2)(η2-C5H 7)}(I-closo-CB11H6Br6), which contain bound weakly coordinating anions, are reported. While thermochemical data show that enthalpically [I-closo-CB11H6Br 6]- binds less strongly with the metal fragment and it is the large entropy loss for the overall process of coordination of the [BAr 4F]- anion that results in the latter anion being thermodynamically more weakly coordinating. Qualitative kinetic data arising from reaction with H2 indicates that the carborane anion is displaced more readily, attributable to the ability of the carborane to lift a Rh-Br interaction.