Supporting Information PlaceholderWe report the incorporation of sulfur, selenium, and tellurium into covalent organic frameworks (COFs). We show that when the larger, more polarizable chalcogens selenium and tellurium are present, the bulk pellet conductivity of the respective COFs increases relative to the sulfur analog by two and almost three orders of magnitude, respectively. These results demonstrate the positive effect of the heavier chalcogens on the electrical properties of COFs and provide a blueprint for the synthesis of similar materials in this class.

A new method for generating uranium alkyl complexes is described. Although homoleptic uranium alkyl complexes are notoriously unstable and difficult to work with, by generating such species in situ, a wide range of alkyl complexes can be accessed from UI(3)(THF)(4).

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The electronic structure of several mono(1,1'diamidoferrocene) uranium complexes (NN R)UX2 (NN R = fc(NR)2, fc = 1,1'-ferrocenediyl, R = SiMe3, Si t BuMe2, SiMe2Ph, X = I, CH2Ph), (NN TBS)UI(OAr) (OAr = 2,6-di-tertbutylphenoxide), and (NN TBS)U(CH2Ph)(OAr) was investigated by electrochemistry, electronic absorption and vibrational spectroscopy, and DFT calculations. Similar metrical parameters were observed for (NN TBS)U(CH2Ph)2 and (NN DMP)U(CH2Ph)2 (and also for the previously reported (NN TMS)UI2(THF), (NN TBS)UI2(THF), and (NN TBS)U(CH2Ph)(OAr)) that translate in similar DFT parameters (bond orders, metal charges) despite some small differences observed by electrochemistry and IR or electronic absorption spectroscopy.

The reactivity of a uranium dibenzyl complex supported by a ferrocenediamide ligand toward aromatic N-heterocycles was investigated. The uranium dibenzyl complex reacted with 1 equiv of pyridine or picoline to give the respective ortho-metalated product. In turn, the eta(2)-N,C-pyridyl complexes reacted with benzoxazole or benzothiazole, leading to a cascade of transformations that involves C-C coupling of the two heterocyclic rings, ring opening, and alkyl transfer. A similar cascade was previously reported for 1-methylimidazole. The present results provide support for the mechanism proposed earlier and attest to the generality of the reaction cascade described.