5 years ago

Synthesis, Electronic Structure, and Reactivities of Two-Sulfur-Stabilized Carbones Exhibiting Four-Electron Donor Ability

Synthesis, Electronic Structure, and Reactivities of Two-Sulfur-Stabilized Carbones Exhibiting Four-Electron Donor Ability
Ryo Iijima, Shigeru Nagase, Tomohito Morosaki, Wei-Wei Wang, Takayoshi Fujii, Tsubasa Suzuki
Bis(sulfane)carbon(0) (BSC; Ph2SCSPh2 (1)) is successfully synthesized by deprotonation of the corresponding protonated salt 1⋅HTfO. The diprotonated salt 1⋅(HTfO)2 as the starting material can be also easily accessed by the deimination of iminosulfane(sulfane)carbon(0) (iSSC)⋅HBF4. Density functional theory calculations revealed the peculiar electronic structure of 1, which has two lone pairs of electrons at the central carbon atom. The largest proton affinities (PA(1): 297.5 kcal mol−1; PA(2): 183.7 kcal mol−1) and the highest energy levels of the HOMOs (HOMO: −4.89 eV; HOMO−1: −5.02 eV) for 1 among the two-sulfur-stabilized carbones clearly indicate the strong donor ability of carbon center stabilized by two SII ligands. The donating ability of these lone pairs of electrons is demonstrated by the C-diaurated and C-proton-aurated complexes, which provide the first experimental evidence for two-sulfurstabilized carbones behaving as four-electron donors. Furthermore, the syntheses and application of AgI carbone complexes as carbone transfer agents are also reported. Two-sulfur-carbone family: The first bis(sulfane)carbone(0) (BSC) is accessed by the deprotonation of the corresponding protonated salt. The strongest donor ability of BSC among the two-sulfur-stabilized carbones results in the diprotonated salt BSC⋅H2. The four-electron donating ability of the two-sulfur-stabilized carbones is demonstrated by the structural analysis of aurated complexes.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201700863

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.