Lithium Bis(trimethylsilyl) Phosphate as a Novel Bifunctional Additive for High-Voltage LiNi1.5Mn0.5O4/Graphite Lithium-Ion Batteries.

The beneficial role of lithium bis(trimethylsilyl) phosphate (LiTMSP), which may act as a novel bifunctional additive for high-voltage LiNi1.5Mn0.5O4 (LNMO)/graphite cells, has been investigated. LiTMSP is synthesized by heating tris(trimethylsilyl) phosphate with lithium tert-butoxide. The cycle performance of LNMO/graphite cells at 45 °C significantly improved upon incorporation of LiTMSP (0.5 wt %). Nuclear magnetic resonance analysis suggests that the trimethylsilyl (TMS) group in LiTMSP can react with hydrogen fluoride (HF), which is generated through the hydrolysis of lithium hexafluorophosphate (LiPF6) by residual water in an electrolyte solution or water generated via oxidative electrolyte decomposition reactions to form TMS fluoride. Inhibition of HF leads to a decrease in the concentration of transition-metal ion-dissolution (Ni and Mn) from the LNMO electrode, as determined by inductively coupled plasma mass spectrometry. In addition, the generation of the superior passivating surface film derived by LiTMSP on the graphite electrode, suppressing further electrolyte reductive decomposition as well as deterioration/reformation caused by migrated transition metal ions, is supported by a combination of chronoamperometry, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy. Furthermore, a LiTMSP-derived surface film has better lithium ion conductivity with a decrease in resistance of the graphite electrode, as confirmed by electrochemical impedance spectroscopy, leading to improvement in the rate performance of LNMO/graphite cells. The HF-scavenging and film-forming effects of LiTMPS are responsible for the less polarization of LNMO/graphite cells enabling improved cycle performance at 45 °C.

C-H addition reactivity of 2-phenylpyridine and 2,2'-bipyridine with pentaphenylborole.

The reactions of pentaphenylborole with pyridines with a pendent aryl group in the 2-position, specifically 2-phenylpyridine and 2,2'-bipyridine, readily afforded adducts. Upon thermolysis, the adducts converted to ortho C-H addition products with the two substituents introduced onto the diene on the boracyclic carbon atoms adjacent to boron in a syn fashion. Photolysis of the syn 2-phenypyridine product led to isomerization to the anti conformer which did not readily occur for the 2,2'-bipyridine complex. Such C-H bond reactivity is uncommon for main group elements and provides insight into methodologies to access boron frameworks.

Isomer Dependence on the Reactivity of Diazenes with Pentaphenylborole.

Reactions of the anti-aromatic pentaphenylborole with diazenes indicate that both the substitution and the isomer influence the reaction outcome. With respect to trans isomers, azobenzene underwent coordination and C-H addition across the diene of the borole, and 2',6'-dimethylazobenzene furnished a fused tricyclic system. Under photolytic conditions, both of the aforementioned diazenes generate the first 1,3,2-diazaborepin heterocycles, rationalized through reactivity with the cis isomers. This notion is corroborated by the reaction of pentaphenylborole with benzo[c]cinnoline, the tethered variant of azobenzene, that only exists as the cis conformer as the corresponding 1,3,2-diazaborepin was produced regardless if the reaction is conducted in the dark or light. The more aromatic pyridazine proved to be less reactive, forming a resilient adduct.

Regioselective oxidation and metalation of meso-unsubstituted azuliporphyrins.

Azuliporphyrins are intriguing porphyrin analogues that incorporate an azulene ring in place of a pyrrolic unit. This system undergoes regioselective oxidation reactions and favors the formation of stable organometallic derivatives. Reaction of meso-unsubstituted azuliporphyrins with Co2(CO)8 or CoCl2·6H2O gave 21-oxyazuliporphyrins, while Cu(OAc)2 produced the corresponding copper(ii) complexes. Treatment of an oxyazuliporphyrin with Ni(OAc)2 or Pd(OAc)2 afforded analogous nickel(ii) and palladium(ii) derivatives. Silver(i) acetate in pyridine reacted with azuliporphyrins to give moderate yields of silver(iii) benzocarbaporphyrins, and the prevalence of structures with a formyl moiety at the sterically crowded 21-position suggested that the ring contraction reactions were triggered in part by intramolecular attack from an axial peroxide ligand. Related thiaazuliporphyrins reacted with palladium(ii) acetate to give palladium(ii) benzothiacarbaporphyrins but this chemistry did not give rise to structures with 21-formyl groups, suggesting that the ring contraction reactions occurred by a different mechanistic pathway. These results demonstrate the existence of a rich tapestry of oxidation and metalation reactions for azuliporphyrin systems.

Rhodium(i), rhodium(iii) and iridium(iii) carbaporphyrins.

Treatment of a benzocarbaporphyrin with [Rh(CO)2Cl]2 in refluxing dichloromethane gave a rhodium(i) dicarbonyl complex, and further reaction in refluxing pyridine afforded an organometallic rhodium(iii) derivative. The carbaporphyrin also reacted with [Ir(COD)Cl]2 and pyridine in refluxing p-xylene to generate a related iridium(iii) compound. These novel metalated porphyrinoids retained strongly diatropic characteristics and were fully characterized by XRD.

Fluorinated triazapentadienyl ligand supported ethyl zinc(ii) complexes: reaction with dioxygen and catalytic applications in the Tishchenko reaction.

Ethyl zinc complexes [N{(C3F7)C(Dipp)N}2]ZnEt, [N{(C3F7)C(Cy)N}2]ZnEt, [N{(CF3)C(2,4,6-Br3C6H2)N}2]ZnEt and [N{(C3F7)C(2,6-Cl2C6H3)N}2]ZnEt have been synthesized from the corresponding 1,3,5-triazapentadiene and diethyl zinc. X-ray data show that [N{(C3F7)C(Dipp)N}2]ZnEt has a distorted trigonal planar geometry at the zinc center. The triazapentadienyl ligand binds to zinc in a κ(2)-mode. The zinc-ethyl bonds of [N{(C3F7)C(Dipp)N}2]ZnEt, [N{(C3F7)C(Cy)N}2]ZnEt, [N{(CF3)C(2,4,6-Br3C6H2)N}2]ZnEt and [N{(C3F7)C(2,6-Cl2C6H3)N}2]ZnEt readily undergo oxygen insertion upon exposure to dry air to produce the corresponding zinc-ethoxy or zinc-ethylperoxy compounds. The ethoxy zinc adducts {[N{(CF3)C(2,4,6-Br3C6H2)N}2]ZnOEt}2 and {[N{(C3F7)C(2,6-Cl2C6H3)N}2]ZnOEt}2 as well as the ethylperoxy zinc adduct {[N{(C3F7)C(Cy)N}2]ZnOOEt}2 have been isolated and fully characterized by several methods including X-ray crystallography. They feature dinuclear structures with four-coordinate zinc sites and bridging-ethoxy or -ethylperoxy groups. The ethyl zinc complexes catalyze the Tishchenko reaction of benzaldehyde under solventless conditions affording benzyl benzoate. The reaction of ethyl zinc complexes with dioxygen and their catalytic behaviour in the Tishchenko reaction are affected by the electronic and steric factors of the triazapentadienyl ligand. {[N{(C3F7)C(Cy)N}2]ZnOOEt}2 is an excellent reagent for the epoxidation of trans-chalcone.

Copper(I), silver(I) and gold(I) complexes of N-heterocyclic carbene-phosphinidene.

N-heterocyclic carbene stabilized phosphinidene IMes·PPh has been used as a bridging ligand to isolate a group of closely related molecules involving all three coinage metal ions. The bis-copper(I) chloride, bis-silver(I) chloride and bis-copper(I) bromide adducts of IMes·PPh crystallize as halide ion bridged octanuclear molecules while the [IMes·PPh](AuCl)2 adduct remains monomeric. These molecules feature long P-C(carbene) bonds in the range 1.822(3)-1.843(4) Å, near the typical P-C single bond length region.

End-on and side-on π-acid ligand adducts of gold(I): carbonyl, cyanide, isocyanide, and cyclooctyne gold(I) complexes supported by N-heterocyclic carbenes and phosphines.

N-heterocyclic carbene ligand SIDipp (SIDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) and trimesitylphosphine ligand have been used in the synthesis of gold(I) cyanide, t-butylisocyanide, and cyclooctyne complexes (SIDipp)Au(CN) (3), (Mes(3)P)Au(CN) (4), [(Mes(3)P)(2)Au][Au(CN)(2)] (5), [(SIDipp)Au(CN(t)Bu)][SbF(6)] ([6][SbF(6)]), [(SIDipp)Au(cyclooctyne)][SbF(6)] ([8][SbF(6)]), and [(Mes(3)P)Au(cyclooctyne)][SbF(6)] ([9][SbF(6)]). A detailed computational study has been carried out on these and the related gold(I) carbonyl adducts [(SIDipp)Au(CO)][SbF(6)] ([1][SbF(6)]), [(Mes(3)P)Au(CO)][SbF(6)] ([2][SbF(6)]), and [(Mes(3)P)Au(CN(t)Bu)](+) ([7](+)). X-ray crystal structures of 3, 5, [6][SbF(6)], [8][SbF(6)], and [9][SbF(6)] revealed that they feature linear gold sites. Experimental and computational data show that the changes in π-acid ligand on (SIDipp)Au(+) from CO, CN(-), CN(t)Bu, cyclooctyne as in [1](+), 3, [6](+), and [8](+) did not lead to large changes in the Au-C(carbene) bond distances. A similar phenomenon was also observed in Au-P distance in complexes [2](+), 4, [7](+), and [9](+) bearing trimesitylphosphine. Computational data show that the Au-L bonds of "naked" [Au-L](+) or SIDipp and Mes(3)P supported [Au-L](+) (L = CO, CN(-), CN(t)Bu to cyclooctyne) have higher electrostatic character than covalent character. The Au←L σ-donation and Au→L π-back-donation contribute to the orbital term with the former being the dominant component, but the latter is not negligible. In the Au-CO adducts [1](+)and [2](+), the cationic gold center causes the polarization of the C-O σ and π orbitals toward the carbon end making the coefficients at the two atoms more equal which is mainly responsible for the large blue shift in the CO stretching frequency. The SIDipp and Mes(3)P supported gold(I) complexes of cyanide and isocyanide also exhibit a significant blue shift in υ(CN) compared to that of the free ligands. Calculated results for Au(CO)Cl and Au(CF(3))CO suggest that the experimentally observed blue shift in ν(CO) of these compounds may at least partly be caused by intermolecular forces.