Nanosized Carbon Macrocycles Based on a Planar Chiral Pseudo Meta-[2.2]Paracyclophane.

Structural designs combining cycloparaphenylenes (CPPs) backbone with planar chiral [2.2]paracyclophane ([2.2]PCP) lead to optical-active chiral macrocycles with intriguing properties. X-ray crystal analysis revealed aesthetic necklace-shaped structures and size-dependent packages with long-range channels. The macrocycles exhibit unique photophysical properties with high fluorescence quantum yield of up to 82 %, and the fluorescent color varies with ring size. In addition, size-dependent chiroptical properties with moderately large CPL dissymmetry factor of 10-3 and CPL brightness in the range of 30-40 M-1 cm-1 were observed.

Drosera-Inspired Dual-Actuating Double-Layer Hydrogel Actuator.

Drosera is a small insectivorous plant whose antennae can fold up, encircle, and prey. The rapid movement of the antennae is achieved by the synergistic effect of a double-layer structure with the antennae contracts on the front and expands on the back. In this work, a drosera-inspired dual-actuating double-layer hydrogel actuator is proposed, in which the temperature-responsive poly(N, N-diethyl acrylamide) (PDEAAm) layer acts as the main actuation layer and a moisture-responsive poly(acrylamide) (PAAm) layer acts as the auxiliary actuation layer. In a water environment with low temperature, both the PAAm and PDEAAm layers absorb water and expand with a swelling property. When the temperature exceeds the lower critical solution temperature of PDEAAm, the PDEAAm layer undergoes a hydrophilic-hydrophobic transition and shrinks rapidly. Therefore, the synergistic effect of the double-layer hydrogel enables the double-layer hydrogel to achieve a large bending angle at high temperature. In addition, when designing and fabricating shape-patterned double-layer hydrogels, complex shape changes can be achieved. Due to the physical and chemical properties, the actuator can be used to grab, transport, and release objects. This drosera-inspired double-layer hydrogel actuator has high practical value, which may provide new insights for the design and manufacture of artificial intelligence materials.

Terminal Thiolate-Dominated H/D Exchanges and H2 Release: Diiron Thiol-Hydride.

To determine the reaction pathways at a metal-ligand site in enzymes, we incorporated a terminal thiolate site into a diiron bridging hydride. Trithiolato diiron hydride, (µ-H)Fe2(pdt)(dppbz)(CO)2(SR) (1(µ-H)) [pdt2- = 1,3-(CH2)3S22-, dppbz = 1,2-C6H4(PPh2)2, RS- = 1,2-Cy2PC6H4S-)], was synthesized directly by photoassisted oxidative addition of 1,2-Cy2PC6H4SH to Fe2(pdt)(dppbz)(CO)4. The terminal thiolate in 1(µ-H) undergoes protonation, affording a thiol-hydride complex [1(µ-H)H]+. Placing an acidic SH site adjacent to the Fe-H-Fe site allows intramolecular thiol-hydride coupling and releases H2 from [1(µ-H)H]+. A diiron η2-H2 intermediate in the formation of H2 is proposed, and is evidenced by the H/D exchange reactions of [1(µ-H)H]+ with D2, D2O, and CD3OD. Isotopic exchange in [1(µ-D)H]+ is driven by an equilibrium isotope effect with 2.1 kJ/mol difference in free energy that favors [1(µ-H)D]+. [1(µ-H)H]+ catalyzes H/D scrambling between H2 and D2O or CD3OD to produce HD. The reactions based on such a "proton-hydride" model provide insights into the reversible heterolytic cleavage of H2 by H2ases.

Gold-Catalyzed Cyclization/Hydroboration of 1,6-Enynes: Synthesis of Bicyclo[3.1.0]hexane Boranes.

The gold-catalyzed cyclization/hydroboration of 1,6-enynes offers facile, versatile, and atom-economical one-step access to bicyclo[3.1.0]hexane boranes. This new protocol proceeds in moderate to good yields under mild conditions. Different from bicyclo[3.1.0]hexane borates, these products are stable in air and during chromatography. Moreover, the borane moiety of the products can readily undergo a diverse array of transformations. The kinetic isotope effect experiment indicates that the hydrogen-transfer step is a fast process, which is not involved in the rate-limiting step.

Dehydrogenation of iron amido-borane and resaturation of the imino-borane complex.

We report on the first isolation and structural characterization of an iron phosphinoimino-borane complex Cp*Fe(η2-H2B[double bond, length as m-dash]NC6H4PPh2) by dehydrogenation of iron amido-borane precursor Cp*Fe(η1-H3B-NHC6H4PPh2). Significantly, regeneration of the amido-borane complex has been realized by protonation of the iron(ii) imino-borane to the amino-borane intermediate [Cp*Fe(η2-H2B-NHC6H4PPh2)]+ followed by hydride transfer. These new iron species are efficient catalysts for 1,2-selective transfer hydrogenation of quinolines with ammonia borane.

Controlled partial transfer hydrogenation of quinolines by cobalt-amido cooperative catalysis.

Catalytic hydrogenation or transfer hydrogenation of quinolines was thought to be a direct strategy to access dihydroquinolines. However, the challenge is to control the chemoselectivity and regioselectivity. Here we report an efficient partial transfer hydrogenation system operated by a cobalt-amido cooperative catalyst, which converts quinolines to 1,2-dihydroquinolines by the reaction with H3N·BH3 at room temperature. This methodology enables the large scale synthesis of many 1,2-dihydroquinolines with a broad range of functional groups. Mechanistic studies demonstrate that the reduction of quinoline is controlled precisely by cobalt-amido cooperation to operate dihydrogen transfer from H3N·BH3 to the N=C bond of the substrates.

Bimetallic nickel-cobalt hydrides in H2 activation and catalytic proton reduction.

The synergism of the electronic properties of nickel and cobalt enables bimetallic NiCo complexes to process H2. The nickel-cobalt hydride [(dppe)Ni(pdt)(H)CoCp*]+ ([1H]+ ) arising from protonation of the reduced state 1 was found to be an efficient electrocatalyst for H2 evolution with Cl2CHCOOH, and the oxidized [Ni(ii)Co(iii)]2+ form is capable of activating H2 to produce [1H]+ . The features of stereodynamics, acid-base properties, redox chemistry and reactivity of these bimetallic NiCo complexes in processing H2 are potentially related to the active site of [NiFe]-H2ases.

Reactivity of the diphosphinodithio ligated nickel(0) complex toward alkyl halides and resultant nickel(i) and nickel(ii)-alkyl complexes.

Diphosphinodithio ligated complexes of nickel(0), nickel(i) and nickel(ii)-alkyl with a reactivity relevant to the C-C bond formation were described. Stoichiometric reactions of the nickel(0) complex, [(P2S2)Ni] ([1]0, P2S2 = (Ph2PC6H4CH2S)2(C2H4)), with alkyl halides (RX) such as C6H5CH2Br, C2H3CH2Br, C2H5I and (CH3)2CHI were investigated, from which the products were found to be highly dependent on the nature of RX used. Oxidative addition of C2H3CH2Br to [1]0 provides the stable Ni(ii)-alkyl complexes [1-allyl]+. The reaction of [1]0 with C6H5CH2Br proceeds through a radical pathway resulting in the formation of the nickel(i) complex [1]+ and an organic homo-coupled product 1,2-diphenylethane. Oxidative addition of C2H5I or (CH3)2CHI to [1]0 can be achieved but it competes with the halogen atom abstraction reaction as found for C6H5CH2Br. [1]0 was shown to be an active catalyst for the coupling reactions of primary halides and alkyl Grignard reagents.