88083-37-8Relevant academic research and scientific papers
Electrochemical studies of dimeric rhodium(III) porphyrins containing a dibasic nitrogen-heterocyclic bridging ligand
Liu,Anderson,Kadish
, p. 2320 - 2325 (2008/10/08)
The electrochemistry and spectroelectrochemistry of [(P)RhCl]2L, where P is the dianion of tetraphenylporphyrin (TPP) or octaethylporphyrin (OEP) and L is a conjugated dibasic nitrogen-heterocyclic ligand such as 4,4′-bipyridine (bpy) or trans-1,2-bis(4-pyridyl)ethylene (BPE) or a nonconjugated nitrogen-heterocyclic ligand such as 1,2-bis(4-pyridyl)ethane (BPA) or 4,4′-trimethylenebis(pyridine) (TMDP), are reported. The Rh(III) dimers with BPA or TMDP nonconjugated bridging ligands undergo one irreversible metal-centered reduction in tetrahydrofuran or methylene chloride. However, two overlapping irreversible metal center reductions are observed for Rh(III) dimers that are linked via the conjugated bridging ligands, bpy and BPE. In all cases, [(P)Rh]2 and the free nitrogen-heterocyclic ligand are generated as products from one or more chemical reactions that follow the metal-centered reduction of Rh(III) to Rh(II). Two reversible two-electron oxidations are observed for [(P)RhCl]2L, where L = BPE, BPA, and TMDP. This contrasts with the case for [(P)RhCl]2bpy, which undergoes a single reversible two-electron transfer followed by two reversible one-electron oxidations. On the basis of the electrochemical and spectroelectrochemical data, an overall mechanism for reduction and oxidation of the [(P)RhCl]2L complexes is presented.
Organometallic chemistry of rhodium tetraphenylporphyrin derivatives: Formyl, hydroxymethyl, and alkyl complexes
Wayland, Bradford B.,Van Voorhees, Seth L.,Wilker, Charles
, p. 4039 - 4042 (2008/10/08)
Organometallic reactivity patterns of the rhodium tetraphenylporphyrin derivatives Rh(TPP)(H), Rh(TPP)-, and (Rh(TPP))2 are found to closely parallel those of the corresponding rhodium octaethylporphyrin species. Preparation and physical properties of the formyl, hydroxymethyl, and alkyl complexes of Rh(TPP) are described along with the photoinduced insertion of carbon monoxide into the Rh-CH3 bond. Thermodynamic values for the reaction Rh(TPP)(H) + CO ? Rh(TPP)(CHO) in C6D6 are ΔH° = -42 kJ/mol and ΔS° = -89 ± 15 J/(K mol).
