3 years ago

Synthesis and Characterization of Bioinspired [Mo2Fe2]–Hydride Cluster Complexes and Their Application in the Catalytic Silylation of N2

Synthesis and Characterization of Bioinspired [Mo2Fe2]–Hydride Cluster Complexes and Their Application in the Catalytic Silylation of N2
Mizuki Tada, Yuna Araki, Yoichi Sakai, Yasuhiro Ohki
The hydride-supported [Mo2Fe2] cluster complex {Cp*Mo(PMe3)}2{FeN(SiMe3)2}2(H)8 (2 a; Cp*=η5-C5Me5) and its [Mo2Mn2] congener 2 b were synthesized from the reactions of Cp*Mo(PMe3)(H)5 (1) with M{N(SiMe3)2}2 (M=Fe, Mn). The amide-to-thiolate ligand-exchange reactions of complex 2 a with bulky thiol reagents (HSR; R=2,4,6-iPr3C6H2 (Tip), 2,6-(SiMe3)2C6H3 (Btp)) furnished the corresponding hydride-supported [Mo2Fe2](SR)2 cluster complexes. The [Mo2Fe2] clusters served as catalyst precursors for the reductive silylation of N2 and yielded ≈65–69 equivalents of N(SiMe3)3 relative to the [Mo2Fe2] clusters. Treatment of complexes 2 a and b with an excess of CNtBu resulted in the formation of dinuclear Mo−Fe and Mo−Mn complexes, which indicated that the [Mo2M2] cores (M=Fe, Mn) split into two dinuclear species upon accommodation of substrates. Reduction of N2: Taking inspiration from the biological process, hydride-supported [Mo2Fe2] cluster complexes are synthesized, characterized, and successfully used as catalyst precursors for the reductive silylation of N2 (see scheme).

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

DOI: 10.1002/chem.201702925

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.