Issue 2, 2015

Redox activity and π bonding in a tripodal seven-coordinate molybdenum(vi) tris(amidophenolate)

Abstract

A tris(aminophenol), tris(2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)amino-4-methylphenyl)amine, MeClampH6, is prepared in three steps from tri-p-tolylamine. The ligand reacts with dioxomolybdenum(VI) bis(acetylacetonate) to form an oxo-free heptadentate complex, (MeClamp)Mo, with a capped octahedral geometry. The molybdenum is formally in the +6 oxidation state, with significant π donation of the amidophenolates, as judged by intraligand bond distances. Two ligand-based oxidations and one metal-centered reduction are observed by cyclic voltammetry. Analysis of the optical spectrum of the compound gives an estimate of the energetic stabilization of the ligand π orbitals by bonding to the molybdenum of approximately 0.9 eV, corresponding to about 40 kcal mol−1 per π bond.

Graphical abstract: Redox activity and π bonding in a tripodal seven-coordinate molybdenum(vi) tris(amidophenolate)

Supplementary files

Article information

Article type
Paper
Submitted
24 Sep 2014
Accepted
23 Oct 2014
First published
04 Nov 2014

Dalton Trans., 2015,44, 677-685

Author version available

Redox activity and π bonding in a tripodal seven-coordinate molybdenum(VI) tris(amidophenolate)

T. Marshall-Roth and S. N. Brown, Dalton Trans., 2015, 44, 677 DOI: 10.1039/C4DT02936D

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