Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 3, 2015
Previous Article Next Article

SO2 – yet another two-faced ligand

Author affiliations

Abstract

Experimentally known adducts of SO2 with transition metal complexes have distinct geometries. In the present paper, we demonstrate by a bonding analysis that this is a direct consequence of sulfur dioxide acting as an acceptor in one set, square-planar complexes of d8 and linear two-coordinated complexes of d10 transition metals, and as a donor with other compounds, well-known paddle-wheel [Rh2(O2CCF3)4] and square-pyramidal [M(CO)5] (M = Cr, W) complexes. Bonding energy computations were augmented by the natural bond orbital (NBO) analysis and energy decomposition analysis (EDA). When the SO2 molecule acts as an acceptor, bonding in the bent coordination mode to the axial position of the d8 or the d10 metal center, the dominant contributor to the bonding is LAO(S) (Lewis Acidic Orbital, mainly composed of the px-orbital of the S atom) as an acceptor, while a dz2 orbital centered on the metal is the corresponding donor. In contrast, the distinct collinear (or linear) coordination of the SO2 bound at the axial position of [Rh2(O2CCF3)4] and/or [M(CO)5] is associated with a dominant donation from a lone pair localized on the sulfur atom, σ*(Rh–Rh) and/or empty LAO(M) (mainly composed of the dz2 orbital of the metal), respectively, acting as an acceptor orbital. The donor/acceptor capabilities of the SO2 molecule were also checked in adducts with organic Lewis acids (BH3, B(CF3)3) and Lewis bases (NH3, N(CH3)3, N-heterocyclic carbene).

Graphical abstract: SO2 – yet another two-faced ligand

Back to tab navigation

Supplementary files

Article information


Submitted
18 Sep 2014
Accepted
01 Dec 2014
First published
01 Dec 2014

Phys. Chem. Chem. Phys., 2015,17, 1987-2000
Article type
Paper
Author version available

SO2 – yet another two-faced ligand

J. Li and A. Yu. Rogachev, Phys. Chem. Chem. Phys., 2015, 17, 1987
DOI: 10.1039/C4CP04208E

Social activity

Search articles by author

Spotlight

Advertisements