Stibasilene SbSi and Its Lighter Homologues: A Comparative Study

The multiply bonded derivatives of the heavier main group elements are among the most challenging targets for synthetic pursuits. Those of them featuring a double bond between the silicon and group 15 element are represented mostly by the silaimines <i>N</i>Si< and phosphasilenes PSi< with a very few examples of arsasilenes AsSi<. In this contribution, we report on the synthesis and structural elucidation of the first stable stibasilene and novel phosphasilene and arsasilene derivatives, featuring an identical substitution pattern. A systematic comparison within the series phosphasilene–arsasilene–stibasilene is made on the basis of their experimental and computational studies

Stibasilene SbSi and Its Lighter Homologues: A Comparative Study

The multiply bonded derivatives of the heavier main group elements are among the most challenging targets for synthetic pursuits. Those of them featuring a double bond between the silicon and group 15 element are represented mostly by the silaimines <i>N</i>Si< and phosphasilenes PSi< with a very few examples of arsasilenes AsSi<. In this contribution, we report on the synthesis and structural elucidation of the first stable stibasilene and novel phosphasilene and arsasilene derivatives, featuring an identical substitution pattern. A systematic comparison within the series phosphasilene–arsasilene–stibasilene is made on the basis of their experimental and computational studies

Pyramidanes: The Covalent Form of the Ionic Compounds

Pyramidane and its derivatives are among the most desirable synthetic chemistry targets, whose appealing square-pyramidal design, fascinating nonclassical structure, and unusual bonding features have attracted the permanently growing interest of organic chemists for decades. Although they have been comprehensively approached on theoretical grounds, no member of the pyramidane family was experimentally realized until very recently, thus remaining one of the biggest synthetic challenges for experimental pursuits. In this paper, we report on a series of stable hybrid pyramidanes of group 14 elements, featuring germanium, tin, or lead at the apex of the square pyramid, capping the four-membered-ring base made of carbon, silicon, or germanium atoms. On the basis of the experimental results (X-ray diffraction and NMR and Mössbauer spectroscopy) and computational studies at the B3LYP/Def2TZVP level of theory (MO, NBO, NRT, and AIM), an extraordinarily high degree of ionicity of the pyramidal apex-to-base bonds was attributed to the overall structure of these nonclassical covalent compounds