Herein we report the first comprehensive series of crystallographically characterised transition metal formyl complexes. In these complexes, the formyl ligand is trapped as part of a chelating structure between a...

Perfluoroalkyl substances (PFAS) are pervasive in the environment. The largest single use material within the PFAS compound class is poly(tetrafluoroethylene) (PTFE), a robust and chemically resistant polymer. Despite their widespread use and serious concerns about their role as pollutants, methods for repurposing PFAS are rare. Here we show that a nucleophilic magnesium reagent reacts with PTFE at room temperature, generating a molecular magnesium fluoride which is easily separated from the surface-modified polymer. The fluoride in turn can be used to transfer the fluorine atoms to a small array of compounds. This proofof-concept study demonstrates that the atomic fluorine content of PTFE can be harvested and reused in chemical synthesis.

Relationships between chemical structure and conductivity in ordered polymers (OPs) are difficult to probe using bulk samples. We propose that conductance measurements of appropriate molecular-scale models can reveal trends in electronic coupling(s) between repeat units that may help inform OP design. Here we apply the scanning tunneling microscope-based break junction (STM-BJ) method to study transport through single-molecules comprising OPrelevant imine, imidazole, diazaborole, and boronate ester dynamic covalent chemical bridges.Notably, solution-stable boron-based compounds hydrolyze in situ unless measured under a rigorously inert glovebox atmosphere. We find that junction conductance correlates with the electronegativity difference between bridge atoms, and corroborative first-principles calculations further reveal a different nodal structure in the transmission eigenchannels of boronate ester junctions. This work reaffirms expectations that highly polarized bridge motifs represent poor choices for the construction of OPs with high through-bond conductivity and underscores the utility of glovebox STM-BJ instrumentation for studies of air-sensitive materials.

Current examples of carbon chain production from metal formyl intermediates with homogeneous metal complexes are described in this Minireview. Mechanistic aspects of these reactions as well as the challenges and opportunities in using this understanding to develop new reactions of CO and H2 are also discussed.

The activation of C–C σ-bonds within strained three- and four-membered hydrocarbons at electrophilic Mg and Zn centres is reported. This was achieved in a two-step process involving (i) hydrometallation of...

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Reaction of a molecular calcium hydride with a series of group 9 dicarbonyl complexes [M(η5-C5Me5)(CO)2] (M = Co, Rh, Ir) led to the formation of both mono(formyl) and bis(formyl) complexes....

Current examples of carbon chain production from metal formyl intermediates with homogeneous metal complexes are described in this Minireview. Mechanistic aspects of these reactions as well as the challenges and opportunities in using this understanding to develop new reactions of CO and H 2 are also discussed.