Rhodium Thiavinyl Carbenes from 1,2,3-Thiadiazoles Enable Modular Synthesis of Multisubstituted Thiophenes

The rhodium-catalyzed transannulation reaction between 1,2,3-thiadiazoles and alkynes, proceeding via intermediacy of the previously unknown Rh thiavinyl carbene, toward a highly efficient and regioselective synthesis of up to fully substituted thiophenes is described

Heck Reaction of Electronically Diverse Tertiary Alkyl Halides

The efficient Pd-catalyzed Heck reaction of diverse tertiary alkyl halides with alkenes has been developed. Unactivated tertiary alkyl halides efficiently react at room temperature under visible light irradiation with no exogenous photosensitizers required. For activated tertiary alkyl halides, the same catalytic system works well without light. These methods offer a general access to electronically diverse alkenes possessing quaternary and functionalized tertiary allylic carbon centers. The substituents at these centers include alkyl-, carbalkoxy-, tosyl-, phosphonyl-, and boronate groups. It was also shown that the end-game mechanism of this transformation may vary depending on the type of the substrates used

Harvesting Water from Air with High-Capacity, Stable Furan-Based Metal–Organic Frameworks

We synthesized two isoreticular furan-based metal–organic frameworks (MOFs), MOF-LA2-1(furan) and MOF-LA2-2(furan) with rod-like secondary building units (SBUs) featuring 1D channels, as sorbents for atmospheric water harvesting (LA = long arm). These aluminum-based MOFs demonstrated a combination of high water uptake and stability, exhibiting working capacities of 0.41 and 0.48 g of water per g of MOF (under isobaric conditions of 1.70 kPa), respectively. Remarkably, both MOFs showed negligible loss in water uptake after 165 adsorption-desorption cycles. These working capacities rival those of MOF-LA2-1(pyrazole), which has a working capacity of 0.55 g of water per g of MOF. The current MOFs stand out for their high water stability as evidenced by 165 cycles of water uptake and release. MOF-LA2-2(furan) is the first aluminum MOF to employ a double \u27long arm\u27 extension strategy, confirmed through single-crystal X-ray diffraction (SCXRD). The MOFs were synthesized using a straightforward synthesis route. This study offers valuable insights into designing durable, water-stable MOFs and underscores their potential for efficient water harvesting

MOF Linker Extension Strategy for Enhanced Atmospheric Water Harvesting

A linker extension strategy for generating metal–organic frameworks (MOFs) with superior moisture-capturing properties is presented. Applying this design approach involving experiment and computation results in MOF-LA2-1 {[Al(OH)(PZVDC)], where PZVDC2– is (E)-5-(2-carboxylatovinyl)-1H-pyrazole-3-carboxylate}, which exhibits an approximately 50% water capacity increase compared to the state-of-the-art water-harvesting material MOF-303. The power of this approach is the increase in pore volume while retaining the ability of the MOF to harvest water in arid environments under long-term uptake and release cycling, as well as affording a reduction in regeneration heat and temperature. Density functional theory calculations and Monte Carlo simulations give detailed insight pertaining to framework structure, water interactions within its pores, and the resulting water sorption isotherm