Depth-Based Recognition of Shape Outlying Functions

A major drawback of many established depth functionals is their ineffectiveness in identifying functions outlying merely in shape. Herein, a simple modification of functional depth is proposed to provide a remedy for this difficulty. The modification is versatile, widely applicable, and introduced without imposing any assumptions on the data, such as differentiability. It is shown that many favorable attributes of the original depths for functions, including consistency properties, remain preserved for the modified depths. The powerfulness of the new approach is demonstrated on a number of examples for which the known depths fail to identify the outlying functions. Supplementary material for this article is available online.     

CH Activation of Benzene by a Photoactivated NiII(azide): Formation of a Transient Nickel Nitrido Complex

Photochemical activation of nickel‐azido complex 2 [Ni(N₃)(PNP)] (PN^HP=2,2′‐di(isopropylphosphino)‐4,4′‐ditolylamine) in neat benzene produces diamagnetic complex 3 [Ni(Ph)(PN^PN^H)], which is crystallographically characterized. DFT calculations support photoinitiated N₂‐loss of the azido complex to generate a rare, transient Ni^IV nitrido species, which bears significant nitridyl radical character. Subsequent trapping of this nitrido through insertion into the Ni? P bond generates a coordinatively unsaturated Ni^II imidophosphorane P?N donor. This species shows unprecedented reactivity toward 1,2‐addition of a C? H bond of benzene to form 3 . The structurally characterized chlorido complex 4 [Ni(Cl)(PN^PN^H)] is generated by reaction of 3 with HCl or by direct photolysis of 2 in chlorobenzene. This is the first report of aromatic C? H bond activation by a trapped transient nitrido species of a late transition metal.     

Zeolite Synthesis in the Presence of Metallosiloxanes for the Quantitative Encapsulation of Metal Species for the Selective Catalytic Reduction (SCR) of NOx

Metal encapsulation in zeolitic materials through one-pot hydrothermal synthesis (HTS) is an attractive technique to prepare zeolites with a high metal dispersion. Due to its simplicity and the excellent catalytic performance observed for several catalytic systems, this method has gained a great deal of attention over the last few years. While most studies apply synthetic methods involving different organic ligands to stabilize the metal under synthesis conditions, here we report the use of metallosiloxanes as an alternative metal precursor. Metallosiloxanes can be synthesized from simple and cost-affordable chemicals and, when used in combination with zeolite building blocks under standard synthesis conditions, lead to quantitative metal loading and high dispersion. Thanks to the structural analogy of siloxane with TEOS, the synthesis gel stabilizes by forming siloxane bridges that prevent metal precipitation and clustering. When focusing on Fe-encapsulation, we demonstrate that Fe-MFI zeolites obtained by this method exhibit high catalytic activity in the NH₃-mediated selective catalytic reduction (SCR) of NO_x along with a good H₂O/SO₂ tolerance. This synthetic approach opens a new synthetic route for the encapsulation of transition metals within zeolite structures.     

Macrocyclic diorganotin complexes of gamma-amino acid dithiocarbamates as hosts for ion-pair recognition

The dimethyl-, di-n-butyl-, and diphenyltin(IV) dithiocarbamate (dtc) complexes [{R2Sn(L-dtc)}x] 1-7 (1, L = L1, R = Me; 2, L = L1, R = n-Bu; 3, L = L2, R = Me, x = infinity; 4, L = L2, R = n-Bu; 5, L = L3, R = Me, x = 2; 6, L = L3, R = n-Bu, x = 2; 7, L = L3, R = Ph, x = 2) have been prepared from a series of secondary amino acid (AA) homologues as starting materials: N-benzylglycine (alpha-AA derivative = L1), N-benzyl-3-aminopropionic acid (beta-AA derivative = L2), and N-benzyl-4-aminobutyric acid (gamma-AA derivative = L3). The resulting compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR ((1)H, (13)C, and (119)Sn) spectroscopy, thermogravimetric analysis, and X-ray crystallography, showing that in all complexes both functional groups of the heteroleptic ligands are coordinated to the tin atoms. By X-ray diffraction analysis, it could be shown that [{Me2Sn(L2-dtc)}x] (3) is polymeric in the solid state, while the complexes derived from L3 (5-7) have dinuclear 18-membered macrocyclic structures of the composition [{R2Sn(L3-dtc)}2]. For the remaining compounds, it could not be established with certainty whether the structures are macrocyclic or polymeric. A theoretical investigation at the B3LYP/SBKJC(d,p) level of theory indicated that the alpha-AA-dtc complexes might have trinuclear macrocyclic structures. The macrocyclic complexes 5-7 have a double-calix-shaped conformation with two cavities large enough for the inclusion of aliphatic and aromatic guest molecules. They are self-complementary for the formation of supramolecuar synthons that give rise to 1D molecular arrangements in the solid state. Preliminary recognition experiments with tetrabutylammonium acetate have shown that the [{R2Sn(L3-dtc)}2] macrocycles 6 and 7 might interact simultaneously with anions (AcO(-)), which coordinate to the tin atoms, and organic cations (TBA(+)), which accommodate within the hydrophobic cavity (ion-pair recognition).     

Direct,High-Yield Transformation of Tetrahydropyranyl Ethers to Acetates

The practically quantitative transformation of steroidal tetrahydropyranyl ethers to acetates with acetyl chloride in aprotic solvents is described.     

Inter-comparison of 2 microm Heterodyne Differential Absorption Lidar, Laser Diode Spectrometer, LICOR NDIR analyzer and flasks measurements of near-ground atmospheric CO2 mixing ratio

Remote sensing and in situ instruments are presented and compared in the same location for accurate CO(2) mixing ratio measurements in the atmosphere: (1) a 2.064 microm Heterodyne DIfferential Absorption Lidar (HDIAL), (2) a field deployable infrared Laser Diode Spectrometer (LDS) using new commercial diode laser technology at 2.68 microm, (3) LICOR NDIR analyzer and (4) flasks. LDS, LICOR and flasks measurements were made in the same location, LICOR and flasks being taken as reference. Horizontal HDIAL measurements of CO(2) absorption using aerosol backscatter signal are reported. Using new spectroscopic data in the 2 microm band and meteorological sensor measurements, a mean CO(2) mixing ratio is inferred by the HDIAL in a 1 km long path above the 15m height location of the CO(2) in situ sensors. We compare HDIAL and LDS measurements with the LICOR data for 30 min of time averaging. The mean standard deviation of the HDIAL and the LDS CO(2) mixing ratio results are 3.3 ppm and 0.89 ppm, respectively. The bias of the HDIAL and the LDS measurements are -0.54 ppm and -0.99 ppm, respectively.     

N-containing boronic esters as self-complementary building blocks for the assembly of 2D and 3D molecular networks

The combination of two heteroaromatic boronic acids with pentaerythritol gave self-complementary tectons which were suitable for the generation of 2D and 3D molecular networks.