Phosphasilene mediated CO activation and deoxygenative homo coupling of CO molecules in reactions with metal carbonyls

Author(s)
Zohreh Hendi, Renuka Pradhan, Katharina Rachuy, Soheil Mahmoudi, Madhusudan K Pandey, Saroj Kumar Kushvaha, Regine Herbst-Irmer, Upakarasamy Lourderaj, Dietmar Stalke, Herbert W Roesky
Abstract

Herein, we report the synthesis of a new sterically demanding hyper-coordinate phosphasilene (Mes*PSi(SiMe3)(PhC(N t Bu)2) (1) and its unprecedented reactivity with metal carbonyls (M = Fe, Mo, W). The reaction of 1 with Fe(CO)5 involves the deoxygenative homocoupling of two CO molecules, forming a rare ketene (μ-CCO) inserted Fe complex 2. Contrastingly, reactions with M(CO)6 (M = Mo, W) entail the deoxygenated activation of one CO molecule, with the second CO molecule being trapped between Si and P atoms. All the compounds including their crystal structures, are thoroughly characterized and potential energy profiles for the reaction mechanisms are also explored.

Organisation(s)
Department of Inorganic Chemistry, Core Facility Crystal Structure Analysis
External organisation(s)
Georg-August-Universität Göttingen, National Institute of Science Education and Research
Journal
Chemical Science
Volume
15
Pages
18888-18895
No. of pages
8
ISSN
2041-6520
DOI
https://doi.org/10.1039/d4sc05491a
Publication date
2024
Peer reviewed
Yes
Austrian Fields of Science 2012
104003 Inorganic chemistry, 204001 Inorganic chemical technology
ASJC Scopus subject areas
General Chemistry
Portal url
https://ucrisportal.univie.ac.at/en/publications/34861b35-a1ae-4d1f-93c1-817b5a2d828b