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WIREs Comput Mol Sci
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Rh chemistry through the eyes of theory

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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.
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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.
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Partitioning scheme applied to the IMOMO calculations.
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The early steps of a hydroformylation reaction: CO dissociation and olefin coordination. Only the prolinear pathway is considered, and ethene serves as a substrate.
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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.
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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).
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Self‐assembly of 4 in the coordination sphere of a late transition metal ion.
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Structure and Mechanism > Reaction Mechanisms and Catalysis
Structure and Mechanism > Molecular Structures

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