54123-72-7Relevant articles and documents
Isolation and structural characterization of geminal di(iodozincio)methane complexes stabilized with nitrogen ligands
Nishida, Yusuke,Hosokawa, Naoki,Murai, Masahito,Takai, Kazuhiko
, p. 114 - 117 (2015)
Treatment of gem-di(iodozincio)methane with pyridine or diamine derivatives resulted in the isolation of a storable gem-di(iodozincio)methane species. Use of the sterically bulky bipyridine ligand gave a gem-di(iodozincio)methane complex, which allowed the first X-ray structural analysis of such species. This work represents a rare example of the isolation of an organometallic reactive species in Schlenk equilibrium and thus provides new insight into the design of efficient and storable organometallic reagents. The isolated gem-di(iodozincio)methane complexes serve as effective methylene dianion synthons for olefination of carbonyl compounds.
Structural elucidation of a methylenation reagent of esters: Synthesis and reactivity of a dinuclear titanium(iii) methylene complex
Kurogi, Takashi,Kuroki, Kaito,Moritani, Shunsuke,Takai, Kazuhiko
, p. 3509 - 3515 (2021/03/29)
Transmetallation of a zinc methylene complex [ZnI(tmeda)]2(μ-CH2) with a titanium(iii) chloride [TiCl3(tmeda)(thf)] produced a titanium methylene complex. The X-ray diffraction study displayed a dinuclear methylene structure [TiCl(tmeda)]2(μ-CH2)(μ-Cl)2. Treatment of an ester with the titanium methylene complex resulted in methylenation of the ester carbonyl to form a vinyl ether. The titanium methylene complex also reacted with a terminal olefin, resulting in olefin-metathesis and olefin-homologation. Cyclopropanation by methylene transfer from the titanium methylene proceeded by use of a 1,3-diene. The mechanistic study of the cyclopropanation reaction by the density functional theory calculations was also reported.
