Nickel-Mediated Hydrogenolysis of C–O Bonds of Aryl Ethers: What Is the Source of the Hydrogen?

Mechanistic studies of the hydrogenolysis of aryl ethers by nickel were undertaken with (diphosphine)aryl methyl ethers. A Ni(0) complex containing Ni–arene interactions adjacent to the aryl–O bond was isolated. Heating led to aryl–O bond activation and generation of a nickel aryl methoxide complex. Formal β-H elimination from this species produced a nickel aryl hydride which can undergo reductive elimination in the presence of formaldehyde to generate a carbon monoxide adduct of Ni(0). The reported complexes map out a plausible mechanism of aryl ether hydrogenolysis catalyzed by nickel. Investigations of a previously reported catalytic system using isotopically labeled substrates are consistent with the mechanism proposed in the stoichiometric system, involving β-H elimination from a nickel alkoxide rather than cleavage of the Ni–O bond by H_2

Egocentric Activity Recognition with Multimodal Fisher Vector

With the increasing availability of wearable devices, research on egocentric activity recognition has received much attention recently. In this paper, we build a Multimodal Egocentric Activity dataset which includes egocentric videos and sensor data of 20 fine-grained and diverse activity categories. We present a novel strategy to extract temporal trajectory-like features from sensor data. We propose to apply the Fisher Kernel framework to fuse video and temporal enhanced sensor features. Experiment results show that with careful design of feature extraction and fusion algorithm, sensor data can enhance information-rich video data. We make publicly available the Multimodal Egocentric Activity dataset to facilitate future research.Comment: 5 pages, 4 figures, ICASSP 2016 accepte

Combination of Redox-Active Ligand and Lewis Acid for Dioxygen Reduction with π-Bound Molybdenum−Quinonoid Complexes

A series of π-bound Mo−quinonoid complexes supported by pendant phosphines have been synthesized. Structural characterization revealed strong metal–arene interactions between Mo and the π system of the quinonoid fragment. The Mo–catechol complex (2a) was found to react within minutes with 0.5 equiv of O_2 to yield a Mo–quinone complex (3), H_2O, and CO. Si- and B-protected Mo–catecholate complexes also react with O_2 to yield 3 along with (R_2SiO)_n and (ArBO)_3 byproducts, respectively. Formally, the Mo–catecholate fragment provides two electrons, while the elements bound to the catecholate moiety act as acceptors for the O_2 oxygens. Unreactive by itself, the Mo–dimethyl catecholate analogue reduces O_2 in the presence of added Lewis acid, B(C_6F_5)_3, to generate a MoI species and a bis(borane)-supported peroxide dianion, [[(F_5C_6)_3B]_2O_2^(2–)], demonstrating single-electron-transfer chemistry from Mo to the O_2 moiety. The intramolecular combination of a molybdenum center, redox-active ligand, and Lewis acid reduces O_2 with pendant acids weaker than B(C_6F_5)_3. Overall, the π-bound catecholate moiety acts as a two-electron donor. A mechanism is proposed in which O_2 is reduced through an initial one-electron transfer, coupled with transfer of the Lewis acidic moiety bound to the quinonoid oxygen atoms to the reduced O_2 species

Synthesis and C−C Coupling Reactivity of a Dinuclear Ni^I−Ni^I Complex Supported by a Terphenyl Diphosphine

Mono- and bimetallic complexes of nickel supported by a terphenyl diphosphine have been synthesized. The reported complexes show diverse metal−arene interactions in the solid state. Reactions of an o,o′-biphenyldiyl dinickel complex with CO and dichloroalkanes lead to fluorene derivatives, indicating the formation of carbon−carbon bonds at a bimetallic moiety

Cross-Coupling Chemistry at Mononuclear and Dinuclear Nickel Complexes

Nickel catalysts have been developed for a wide range of C–C bond formation reactions. Reaction mechanisms proposed for these transformations generally involve catalytic intermediates based on mononickel species. These reactions are reviewed and the possibility of dinickel species active in C–C cross-coupling chemistry is discussed

Reversible Halide-Modulated Nickel–Nickel Bond Cleavage: Metal–Metal Bonds as Design Elements for Molecular Devices

The dinickel chloride affair: In dinuclear nickel(I) complexes supported by a tris(phosphinoaryl)benzene and stabilized by metal–arene interactions, chloride addition causes reversible Ni-Ni bond cleavage that induces 180° rotation around an aryl–aryl bond (see scheme). A dinickel–chloride moiety was found to rotate around the bridging arene by a mechanism involving breaking and forming Ni-P bonds

An Organocobalt–Carbon Nanotube Chemiresistive Carbon Monoxide Detector

A chemiresistive detector for carbon monoxide was created from single-walled carbon nanotubes (SWCNTs) by noncovalent modification with diiodo(η⁵:η¹-1-[2-(N,N-dimethylamino)ethyl]-2,3,4,5-tetramethylcyclopentadienyl)-cobalt(III) ([Cp[superscript ∧]CoI₂]), an organocobalt complex with an intramolecular amino ligand coordinated to the metal center that is displaced upon CO binding. The unbound amino group can subsequently be transduced chemiresistively by the SWCNT network. The resulting device was shown to have a ppm-level limit of detection and unprecedented selectivity for CO gas among CNT-based chemiresistors. This work, the first molecular-level mechanistic elucidation for a CNT-based chemiresistive detector for CO, demonstrates the efficacy of using an analyte’s reactivity to produce another chemical moiety that is readily transduced as a strategy for the rational design of chemiresistive CNT-based detectors.National Science Foundation (U.S.) (DMR-1410718)National Science Foundation (U.S.) (1122374

Nickel Hydrides Supported by a Non-Innocent Diphosphine Arene Pincer: Mechanistic Studies of Nickel−Arene H-Migration and Partial Arene Hydrogenation

Nickel hydrides supported by a terphenyl diphosphine were synthesized and found to undergo nickel-to-arene H-transfers. Some of the resulting complexes also undergo the reverse (C-to-Ni) H-migration, indicating the potential for storing H-equivalents in this type of pincer ligand. NMR spectroscopy, single crystal X-ray diffraction, and isotopic labeling studies investigating the mechanism of these processes are discussed