31126-46-2Relevant academic research and scientific papers
Tetrahedral versus planar four-coordinate carbon: A sulfonyl-substituted methandiide
Schroeter, Peter,Gessner, Viktoria H.
, p. 11223 - 11227,5 (2012)
Flattened. The mono- and dilithiation of a sulfonyl-substituted phosphane sulfide is reported. The new dilithio methandiide features a distorted carbon environment between the typical tetrahedral and planar arrangement (see figure). This geometry results from geometrical restrictions of the donor functions and can be described by two unusual bonding modes of the lithium atoms with the sp2-hybridized methanide carbon. Copyright
On the structure and ambiphilicity of a sulfonyl substituted α-chloro lithium base
Becker, Julia,Gessner, Viktoria H.
supporting information, p. 4320 - 4325 (2014/03/21)
An α-chloro lithium base stabilised by a sulfonyl and thiophosphinoyl moiety was selectively prepared by lithiation of its protonated precursor and oxidation of the corresponding dilithio methandiide. The carbenoid-like compound was found to be remarkably stable even at room temperature and thus allowed for its spectroscopic characterisation in solution and in the solid state. Its ambiphilic nature was tested and compared with typical carbenoids both experimentally and by computational methods. The electronic stabilisation results in its thermal stability but considerably reduces the ambiphilic character limiting the reactivity patterns generally observed for lithium carbenoids.
Synthesis and electronic structure of carbene complexes based on a sulfonyl-substituted dilithio methandiide
Becker, Julia,Gessner, Viktoria H.
, p. 1310 - 1317 (2014/04/03)
The application of a sulfonyl-substituted dilithio methandiide in the synthesis of carbene complexes was examined. In all cases, the metal carbon interaction was found to be highly polar with only small π-contribution. Hence, the stability of these complexes was found to greatly rely on the coordination ability of the side-arms supporting the metal carbon interaction. As such, the sulfonyl moiety allowed the isolation of a carbene complex with the oxophilic zirconium, which is the first of its kind bearing no (bis)phosphonium ligand framework. On the contrary, complexes with the late transition metals ruthenium and palladium were found to be more labile due to the facile decoordination of the sulfonyl moiety. This results in the opening of a reactive coordination site at the metal center and hence in further reactions such as cyclometalation or sulfur transfer from the thiophosphoryl moiety to the carbenic carbon atom.
