Treatment of 1,3-bis(3'-butylimidazolyl-1'-yl)benzene diiodide with elemental sulfur in the presence of a base produced a bis(N-heterocyclic thione) (NHT) pincer ligand precursor. Its reaction with PdCl2(CH3CN)2 produced chloro[1,3-bis(3'-butylimidazole-2'-thione-κ-S)benzene-κ-C]palladium(ii), a 6,6-fused ring SCS-NHT palladium pincer complex. This air stable compound is, to our knowledge, the first SCS pincer complex that utilizes N-heterocyclic thione (NHT) donor groups. The molecular structures of the ligand precursor and the palladium complex were determined by X-ray crystallography and computational studies provided insight into the interconversion between its rac and meso conformations. The photophysical properties of the complex were established, and its catalytic activity in Suzuki, Heck, and Sonogashira cross-coupling reactions was evaluated.
Two polymeric ladders were synthesized by topochemical polymerization. The critical assemblies with multiple reactive centers were characterized by single crystal X-ray diffraction. Approximately 64% and 70% of the mass of the two polymeric ladders can be derived from biomass, respectively.
A flexible organic sheet spontaneously assembled under mild conditions from a tri-carbamate. By introducing cyclohexyl side chains as 'pillars' between the sheets, a hydrogen bonded organic framework was formed which displayed a capacity for accommodating and releasing guest molecules. The guest size/shape selectivity of the lamellar framework was demonstrated by testing with various guests.
Hydrosilylation catalyzed by a high-valent
nitridoruthenium(VI)
compound, [RuN(saldach)(CH3OH)]+[ClO4]− (1, where saldach is the dianion
of racemic N,N′-cyclohexan-diyl-bis(salicylideneimine))
is described. Using phenylsilane as reductant, a variety of unsaturated
organic substrates, including aldehydes, ketones, and imines, are
effectively reduced to alcohols and amines, respectively, accompanied
by the redistribution of PhSiH3 at silicon. Mechanistic
studies indicate that the catalysis proceeds via silane activation
rather than carbonyl activation, and the silane is likely activated
via multiple pathways, including a radical-based pathway.
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