3 years ago

E–H (E = N and P) Bond Activation of PhEH2 by a Trinuclear Yttrium Methylidene Complex: Theoretical Insights into Mechanism and Multimetal Cooperation Behavior

E–H (E = N and P) Bond Activation of PhEH2 by a Trinuclear Yttrium Methylidene Complex: Theoretical Insights into Mechanism and Multimetal Cooperation Behavior
Yi Luo, Gen Luo, Zhaomin Hou
E–H (E = N and P) bond activation of PhEH2 by a trinuclear yttrium methylidene complex to give a μ3-EPh species has been investigated through DFT calculations. It has been revealed that the reaction involves three major steps, i.e., activation of one of the two E–H bonds, intramolecular isomerization, and the subsequent activation of the second E–H bond. The first E–H bond activation is a mono-metal-assisted σ-bond metathesis (σ-BM) process, while the second E–H bond activation is achieved by the cooperation of three metal sites. The effect of the phenyl group in PhEH2 has also been examined. It has been found that the phenyl group in PhNH2 showed a significant steric effect for the N–H activation, but in the case of PhPH2, such steric effect was not observed. The relatively low energy barriers and significant exergonic feature lead us to predict that the trinuclear yttrium methylidene complex should be also effective for activation of NH3 and PH3. In addition, a general behavior of the activation of C═X (X = O and S) and E–H (E = C, N, and P) bonds by multialkyl-bridged trinuclear rare-earth complexes has been described, which could be beneficial for further studies on the chemical transformations at multimetallic frameworks.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00443

DOI: 10.1021/acs.organomet.7b00443

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.