X-ray absorption spectroscopy systematics at the tungsten L-edge

Jayarathne, U., Chandrasekaran, P., Greene, A. F., Mague, J. T., DeBeer, S., Lancaster, K. M., Sproules, S. and Donahue, J. P. (2014) X-ray absorption spectroscopy systematics at the tungsten L-edge. Inorganic Chemistry, 53(16), pp. 8230-8241. (doi: 10.1021/ic500256a)

Abstract

A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, has been interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W⁰(PMe₃)₆], [W^IICl₂(PMePh₂)₄], [W^IIICl₂(dppe)₂][PF₆] (dppe = 1,2-bis(diphenylphosphino)ethane), [W^IVCl₄(PMePh₂)₂], [W^V(NPh)Cl₃(PMe₃)₂], and [W^VICl₆] correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio (EBR) of the L_3,2-edges and the L₁ rising-edge energy with metal Z_eff, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W^IV(mdt)₂(CO)₂] and [W^IV(mdt)₂(CN)₂]^2– (mdt^2– = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W^IV species. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: 1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Z_eff in the species of interest; 2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS; 3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate the difference between formal oxidation state and metal Z_eff or, as in the case of [W^IV(mdt)₂(CO)₂], add other subtlety by modulating the redox level of other ligands in the coordination sphere.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Sproules, Dr Stephen
• Authors: Jayarathne, U., Chandrasekaran, P., Greene, A. F., Mague, J. T., DeBeer, S., Lancaster, K. M., Sproules, S., and Donahue, J. P.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Inorganic Chemistry
• Publisher: American Chemical Society
• ISSN: 0020-1669
• ISSN (Online): 1520-510X
• Copyright Holders: Copyright © 2014 American Chemical Society
• First Published: First published in Inorganic Chemistry 53(16):8230-8241
• Publisher Policy: Reproduced in accordance with the copyright policy of the publisher