A Two-Coordinate Nickel Imido Complex That Effects C−H Amination

An exceptionally low coordinate nickel imido complex, (IPr*)Ni═N(dmp) (2) (dmp = 2,6-dimesitylphenyl), has been prepared by the elimination of N_2 from a bulky aryl azide in its reaction with (IPr*)Ni(η^6-C_7H_8) (1). The solid-state structure of 2 features two-coordinate nickel with a linear C−Ni−N core and a short Ni−N distance, both indicative of multiple-bond character. Computational studies using density functional theory showed a Ni═N bond dominated by Ni(dπ)−N(pπ) interactions, resulting in two nearly degenerate singly occupied molecular orbitals (SOMOs) that are Ni−N π* in character. Reaction of 2 with CO resulted in nitrene-group transfer to form (dmp)NCO and (IPr*)Ni(CO)_3 (3). Net C−H insertion was observed in the reaction of 2 with ethene, forming the vinylamine (dmp)NH(CH═CH_2) (5) via an azanickelacyclobutane intermediate, (IPr*)Ni{N,C:κ^2-N(dmp)CH_2CH_2} (4)

Review and Meta-Analyses of TAAR1 Expression in the Immune System and Cancers

Since its discovery in 2001, the major focus of TAAR1 research has been on its role in monoaminergic regulation, drug-induced reward and psychiatric conditions. More recently, TAAR1 expression and functionality in immune system regulation and immune cell activation has become a topic of emerging interest. Here, we review the immunologically-relevant TAAR1 literature and incorporate open-source expression and cancer survival data meta-analyses. We provide strong evidence for TAAR1 expression in the immune system and cancers revealed through NCBI GEO datamining and discuss its regulation in a spectrum of immune cell types as well as in numerous cancers. We discuss connections and logical directions for further study of TAAR1 in immunological function, and its potential role as a mediator or modulator of immune dysregulation, immunological effects of psychostimulant drugs of abuse, and cancer progression

Synthesis and Characterization of Three-Coordinate Ni(III)-Imide Complexes

A new family of low-coordinate nickel imides supported by 1,2-bis(di-tert-butylphosphino)ethane was synthesized. Oxidation of nickel(II) complexes led to the formation of both aryl- and alkyl-substituted nickel(III)-imides, and examples of both types have been isolated and fully characterized. The aryl substituent that proved most useful in stabilizing the Ni(III)-imide moiety was the bulky 2,6-dimesitylphenyl. The two Ni(III)-imide compounds showed different variable-temperature magnetic properties but analogous EPR spectra at low temperatures. To account for this discrepancy, a low-spin/high-spin equilibrium was proposed to take place for the alkyl-substituted Ni(III)-imide complex. This proposal was supported by DFT calculations. DFT calculations also indicated that the unpaired electron is mostly localized on the imide nitrogen for the Ni(III) complexes. The results of reactions carried out in the presence of hydrogen donors supported the findings from DFT calculations that the adamantyl substituent was a significantly more reactive hydrogen-atom abstractor. Interestingly, the steric properties of the 2,6-dimesitylphenyl substituent are important not only in protecting the Ni═N core but also in favoring one rotamer of the resulting Ni(III)-imide, by locking the phenyl ring in a perpendicular orientation with respect to the NiPP plane

The equation of state of molybdenum at 1400 °C

Shock compression data to 96 GPa for pure molybdenum, initially heated to 1400 °C, are presented. Finite strain analysis of the data gives a bulk modulus at 1400 °C, K_(0S), of 244 ± 2 GPa and its pressure derivative, K′_(0S), of 4. A fit of shock velocity to particle velocity gives the coefficients of U_S = c_0 + sU_P to be c_0 = 4.77 ± 0.06 km/s and s = 1.43 ± 0.05. From the zero‐pressure sound speed c_0, a bulk modulus of 232 ± 6 GPa is calculated which is consistent with extrapolation of ultrasonic elasticity measurements. The temperature derivative of the bulk modulus at zero pressure, ∂K_(0S)/∂T|_P, is approximately −0.012 GPa/K. A thermodynamic model is used to show that the thermodynamic Grüneisen parameter is proportional to the density and independent of temperature. The Mie–Grüneisen equation of state adequately describes the high‐temperature behavior of molybdenum under the present range of shock loading conditions

NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist

Tables of ^1H and ^(13)C NMR chemical shifts have been compiled for common organic compounds often used as reagents or found as products or contaminants in deuterated organic solvents. Building upon the work of Gottlieb, Kotlyar, and Nudelman in the Journal of Organic Chemistry, signals for common impurities are now reported in additional NMR solvents (tetrahydrofuran-d_8, toluene-d_8, dichloromethane-d_2, chlorobenzene-d_5, and 2,2,2-trifluoroethanol-d_3) which are frequently used in organometallic laboratories. Chemical shifts for other organics which are often used as reagents or internal standards or are found as products in organometallic chemistry are also reported for all the listed solvents

Fluorescence of thermal control coatings on S0069 and A0114

Many of the thermal control surfaces exposed to the space environment during the 5.8 year LDEF mission experienced changes in fluorescence. All of the thermal control coatings flown on LDEF experiments S0069 and A0114 were characterized for fluorescence under ambient conditions. Some of the black coatings, having protective overcoats, appear bright yellow under ultraviolet exposure. Urethane based coatings exhibited emission spectra shifts toward longer wavelengths in the visible range. Zinc oxide pigment based coatings experienced a quenching of fluorescence, while zinc orthotitanate pigment based and other ceramic type coatings had no measurable fluorescence

Fluorescence measurements of the thermal control experiments coatings on LDEF S0069 and A0114

Fluorescence measurements were made on the thermal control coatings from the Long Duration Experiment Facility (LDEF) S0069, Thermal Control Surfaces Experiment (TCSE); and the A0114, Interaction of Atomic Oxygen with Material Surfaces in Low Earth orbit. Fluorescence was observed in two types of thermal control coatings and is attributed to pigments or binders. In addition, fluorescence measurement on the silver Teflon from the front cover of TCSE led to confirmation of damage (cracking) to the metal layers during application