Rhenium Trichloride Dioxide,ReO2Cl3, Preparation and Reactions

A one step synthesis of ReO₂Cl₃ is reported. ReO₂Cl₃ reacts with [(C₂H₅)₄P]⁺Cl^?, forming [(C₂H₅)₄P]⁺[cis–ReO₂Cl₄]^?, a = 1257.0(2), b = 1026.8(2), c = 1277.9(2) pm, β = 106.659(3)°, P2₁/n. Also an unstable NO⁺[ReO₂Cl₄]^? can be obtained from NOCl and ReO₂Cl₃. With the Lewis acid GaCl₃ the zwitter ion [ReO₂Cl₂]⁺[GaCl₄]^? is formed. a = 1184.0(3), b = 829.2(2), c = 1100.8(2) pm, β = 112.98(1)°, P2₁/c.     

CO2‐Sourced α‐Alkylidene Cyclic Carbonates: A Step Forward in the Quest for Functional Regioregular Poly(urethane)s and Poly(carbonate)s

Described is a robust platform for the synthesis of a large diversity of novel functional CO₂‐sourced polymers by exploiting the regiocontrolled ring‐opening of α‐alkylidene carbonates by various nucleophiles. The reactivity of α‐alkylidene carbonates is dictated by the exocyclic olefinic group. The polyaddition of CO₂‐sourced bis(α‐alkylidene carbonate)s (bis‐αCCs) with primary and secondary diamines provides novel regioregular functional poly(urethane)s. The reactivity of bis‐αCCs is also exploited for producing new poly(β‐oxo‐carbonate)s by organocatalyzed polyaddition with a diol. This synthesis platform provides new functional variants of world‐class leading polymer families (polyurethanes, polycarbonates) and valorizes CO₂ as a chemical feedstock.     

Bis(1,3‐dithiol‐2‐ylidene)‐Substituted Subtriazachlorin: A Subphthalocyanine Analogue with Redox Properties

Bis(1,3‐dithiol‐2‐ylidene)‐substituted subtriazachlorin was formed because of an unusual reaction of a 1,3‐dithiole‐2‐one‐fused subphthalocyanine in a triethylphosphite‐mediated tetrathiafulvalene synthesis. In this novel molecule, the bis(1,3‐dithiol‐2‐ylidene)ethane moiety and subtriazachlorin structure are fused, resulting in an electron‐donating ability and broad absorption in the near‐infrared region.