Home
This Title All WIREs
WIREs RSS Feed
How to cite this WIREs title:
WIREs Comput Mol Sci
Impact Factor: 8.127

Rh chemistry through the eyes of theory

Full article on Wiley Online Library:   HTML PDF

Can't access this content? Tell your librarian.

We discuss the properties of Rh and its compounds from a theoretical chemistry perspective. Like its neighbors in the platinum metal group, this element exhibits a remarkable spectrum of catalytic activity both as an elemental metal and as the central ion of transition metal complexes. This property is reflected in a comparatively weak chemical bond dominated by d–p interactions, varying oxidation states and a highly flexible coordination shell. In turn, theoretical methods and their generalization as empirical concepts have to be able to deal with a multitude of binding situations and the strong electron–electron interaction within the Rh valence orbitals. Whereas density functional theory has greatly enhanced the computational accessibility of Rh compounds, quantitative models of catalytic cycles require a more explicit treatment of static electron correlation, such as integrated density functional‐coupled cluster schemes. WIREs Comput Mol Sci 2016, 6:311–320. doi: 10.1002/wcms.1250 This article is categorized under: Structure and Mechanism > Molecular Structures Structure and Mechanism > Reaction Mechanisms and Catalysis
Dissociative mechanism for the replacement of 4‐picoline by pyridine in a square planar rhodium(I) complex.
[ Normal View | Magnified View ]
Free energy surface computed with the two layer CCSD(T):DFT scheme for the hydroformylation with the 6‐DPPon ligand 4. Both prolinear and probranched pathways are shown, but for clarity only structures corresponding to the prolinear pathway are depicted.
[ Normal View | Magnified View ]
Partitioning scheme applied to the IMOMO calculations.
[ Normal View | Magnified View ]
The early steps of a hydroformylation reaction: CO dissociation and olefin coordination. Only the prolinear pathway is considered, and ethene serves as a substrate.
[ Normal View | Magnified View ]
Rhodium catalyzed hydroformylation of 4‐pentenoate anion with ligand 7 and a schematic presentation of the substrate binding to 7 in the transition state for the initial hydrometallation calculated with DFT.
[ Normal View | Magnified View ]
Tandem hydroformylation–hydrogenation sequence enabled by ligand 6 (a) and a schematic presentation of the transition state for the hydride transfer calculated with DFT (b).
[ Normal View | Magnified View ]
Self‐assembly of 4 in the coordination sphere of a late transition metal ion.
[ Normal View | Magnified View ]

Browse by Topic

Structure and Mechanism > Molecular Structures
Structure and Mechanism > Reaction Mechanisms and Catalysis

Access to this WIREs title is by subscription only.

Recommend to Your
Librarian Now!

The latest WIREs articles in your inbox

Sign Up for Article Alerts