Isolation of a Heavier Cyclobutadiene Analogue: 2,4-Digerma-1,3-diphosphacyclobutadiene

The heavier cyclobutadiene analogue 2,4-digerma-1,3-diphosphacyclobutadiene ([L12Ge2P2], 4; L1 = CH{(CMe)(2,6-iPr2C6H3N)}2), featuring a planar Ge2P2 four-membered ring, has been synthesized via the elimination of carbon monoxide from the corresponding phosphaketenyl germylene [L1GePCO] (2) under UV irradiation.

Mechanism, catalysis and predictions of 1,3,2-diazaphospholenes: theoretical insight into highly polarized P–X bonds

Density functional theory (DFT) calculations were carried out to investigate the hydridic character of several main group hydrides. A P-hydrido-1,3,2-diazaphospholene 1f with two π-electron donor amino groups on the heterocyclic skeleton framework performs as a strong hydride donor owing to the significant n(N)–σ*(P–H) hyperconjugation. The natural bond orbital analysis reveals that high π-electron delocalization exists in both 1f and the corresponding stable phosphenium Ef+.

Comprehensive Comparison Between the Gas-phase SN2 Reactions at Carbon and at Nitrogen

As one of the most important chemical reactions, SN2 reactions play a central role in both synthetic chemistry and the development of mechanistic paradigms. Most of the previous attention has centered on substitution at carbon, whereas displacement at nitrogen is clearly less studied and less understood. The SN2@N reactions have enormous synthetic potential, especially in heterocyclic chemistry, which is a cornerstone of medicinal chemistry, and has been receiving increasing attention, both experimentally and computationally.

Synthesis of aromatic ruthenabenzothiophenes via C–H activation of thiophenes

The first ruthenabenzothiophenes have been achieved via the C–H activation of thiophene. These species feature high thermal stability and resistance of a moderate oxidant, which constitute valuable addition to the rare metallaaromatic containing second-row transition metals.!divAbstract

Synthesis of digermylene-stabilized linear tetraboronate and boroxine

Two newly discovered linear compounds tetraboronate and boroxine stabilized by digermylene are reported, which feature a B4O5 chain and a B3O3 ring, respectively. DFT calculations reveal that not only can digermylene stabilize the electron-deficient boron centers, but also increase the energies of the LUMOs of the boron moiety. Our results provide a hint for the development of boronate covalent organic frameworks.