4 years ago

On the kinetics and mechanism of the conversion of Cr(CO) 5 (κ 1 - P -dppm) to Cr(CO) 4 (κ 2 - P , P ′-dppm) (dppm = 1,2-diphenylphosphinomethane): an alternative hypothesis

Robert A. Gossage


The data from a previously reported kinetic evaluation dealing with the conversion of Cr(CO)51-P-dppm) (1: dppm = 1,2-diphenylphosphinomethane) into the corresponding chelated complex Cr(CO)42-P,P′-dppm) (2), via CO loss, is re-evaluated. The conclusion is that the process is more likely to involve a rate-determining step that is first-order in [Cr(CO)51-P-dppm)], as opposed to the previously reported zero-order model as proposed. This implies CO loss from 1, by presumably either an I d or more likely a Dissociative (D: S N 1-type) mechanism, leads to 2. This hypothesis is compared and contrasted to reported data and comparisons are made to similar processes involving related Group VI metal carbonyl species.

Graphical Abstract

\( \mathop {{\text{Cr}}\left( {\text{CO}} \right)_{5} (\upkappa^{1} -P-dppm) + \Delta }\limits_{{\mathbf{1}}} \to \mathop {{\text{Cr}}\left( {\text{CO}} \right)_{4} (\upkappa^{2} -P,P^{{\prime }} {\text{-dppm}}) + {\text{CO}}}\limits_{{\mathbf{2}}} \)

Publisher URL: https://link.springer.com/article/10.1007/s11243-017-0191-3

DOI: 10.1007/s11243-017-0191-3

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.