Issue 45, 2021

Cyclopentadienylmetal group 6 metal carbonyl derivatives with 2-propanoneoximato and related ligands

Abstract

The structures and energetics of species with the stoichiometries (Me2CNO)M(CO)nCp (M = Cr, Mo, W; n = 3, 2, 1; Cp = η5-C5H5) have been studied by density functional theory. The experimental structure Mo2-1S with an NO-dihapto Me2CNO ligand found by X-ray crystallography for (Me2CNO)Mo(CO)2Cp is shown to be the lowest energy isomer by a substantial margin. The expected initial Me2CNOMo(CO)3Cp product from the reaction of NaMo(CO)3Cp with Me2C(NO)Br used to synthesize (Me2CNO)Mo(CO)2Cp is predicted to undergo facile CO dissociation based on ΔH and ΔG values. The energetics of the currently unknown analogous chromium and tungsten systems appear to be similar to that of the molybdenum system. The structures Me2NC(CO)OM(CO)2Cp (M = Cr, Mo, W) with a dimethylcarbamate ligand are much lower energy (Me2CNO)M(CO)3Cp isomers but are clearly not accessible from reactions of the anions CpM(CO)3 with Me2C(NO)Br. The lowest energy structures for the monocarbonyl (Me2CNO)M(CO)Cp are of the type (Me2C[double bond, length as m-dash]N)M(O)(CO)Cp with separate dimethylimino and oxo ligands formed by oxidative addition of the Me2CNO unit to the central metal atom.

Graphical abstract: Cyclopentadienylmetal group 6 metal carbonyl derivatives with 2-propanoneoximato and related ligands

Supplementary files

Article information

Article type
Paper
Submitted
12 Sep 2021
Accepted
21 Oct 2021
First published
21 Oct 2021

New J. Chem., 2021,45, 21092-21099

Cyclopentadienylmetal group 6 metal carbonyl derivatives with 2-propanoneoximato and related ligands

T. M. Dănescu, R. Silaghi-Dumitrescu, A. Lupan and R. B. King, New J. Chem., 2021, 45, 21092 DOI: 10.1039/D1NJ04379J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements