Title

Design, synthesis, and characterization of a sterically encumbered dioxo molybdenum (VI) core

DOI

10.1016/j.ica.2006.10.041

Document Type

Journal Article

Publication Date

4-20-2007

Publication Title

Inorganica Chimica Acta

Volume

360

Issue

6

First Page

2092

Last Page

2099

ISSN

201693

Keywords

Dendrimer, Molybdenum complexes, Oxygen atom transfer reactivity, Redox reactivity

Abstract

Dioxo-MoVI complexes of general formula Tp*MoO2(p-SC6H4Dn) (6a-6c) (where Tp* = hydrotris(3,5-dimethyl-pyrazol-1-yl)borate and Dn = dendritic unit) have been synthesized and characterized by spectroscopy and mass spectrometry. 1H NMR spectra of the metal complexes indicate that the Cs local symmetry about the metal core does not change by the incorporation of dendritic functionality at the thiophenolato ring. Electrochemical data show a ∼20 mV change in the redox potential in the complexes with dendritic ligands suggesting a very small perturbation in the redox orbital, which is also supported by small changes in the electronic spectra. The peak-to peak separation (ΔEp) increases from 125 mV in 6(a) to 240 mV in 6(c), suggesting sluggish electron transfer in molecules with larger dendritic ligands. © 2006 Elsevier B.V. All rights reserved.

Open Access

Green Accepted

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