Aromatic and Benzylic C−H Bond Activation in the System Bis(dicarbonylrhodium(I))- porphyrinate−Hydrocarbon Solvent

Aromatic and Benzylic C−H Bond Activation in the System Bis(dicarbonylrhodium(I))- porphyrinate−Hydrocarbon Solven

Aromatic and Benzylic C−H Bond Activation in the System Bis(dicarbonylrhodium(I))- porphyrinate−Hydrocarbon Solvent

Aromatic and Benzylic C−H Bond Activation in the System Bis(dicarbonylrhodium(I))- porphyrinate−Hydrocarbon Solven

Unexpected Reactivity of Rh(TPP)I(CO) toward an Alkoxide in CH₂Cl₂: Synthesis and Crystal Structure of Rh(TPP)(CH₂Cl)

Unexpected Reactivity of Rh(TPP)I(CO) toward an Alkoxide in CH2Cl2:  Synthesis and Crystal Structure of Rh(TPP)(CH2Cl

Unexpected Reactivity of Rh(TPP)I(CO) toward an Alkoxide in CH₂Cl₂: Synthesis and Crystal Structure of Rh(TPP)(CH₂Cl)

Unexpected Reactivity of Rh(TPP)I(CO) toward an Alkoxide in CH2Cl2:  Synthesis and Crystal Structure of Rh(TPP)(CH2Cl

An Efficient Diamine·Copper Complex-Catalyzed Coupling of Arylboronic Acids with Imidazoles

A novel diamine·copper complex-catalyzed intermolecular coupling of arylboronic acids (1) with imidazoles (3) is described. In the presence of a catalytic amount of [Cu(OH)·TMEDA]2Cl2 (2), arylboronic acids (1) react smoothly with imidazoles (3) in dichloromethane at room temperature to give a variety of N-arylimidazoles (4) in good to excellent yields

Synthesis and Reactivity of Porphyrinatorhodium(II)−Triethylphosphine Adducts: The Role of PEt₃ in Stabilizing a Formal Rh(II) State

Rh(por)H, where por is an octaethyl- or meso−tetraphenylporphyrin dianion, reacts with triethylphosphine to form stable mononuclear paramagnetic formally-RhII complexes, Rh(OEP)(PEt3) and Rh(TPP)(PEt3)2. The former adduct is also obtained as the sole product of the reaction between Rh2(OEP)2 and PEt3. The EPR spectroscopy at 77 K shows both complexes to have mainly porphyrin-based HOMOs. The composition and the reactivity of Rh(TPP)(PEt3)2 support its formulation as RhIII(TPP•-)(PEt3)2. In contrast, Rh(OEP)(PEt3) demonstrates the reactivity of both a RhII d7 center and a porphyrin π-anion radical. The adduct reacts with O2 as a RhII(por) species, originally forming a RhIII-superoxido derivative. In contrast, with water Rh(OEP)(PEt3) reacts as a porphyrin π-anion radical, yielding a RhIII−octaethylphlorin complex. The latter is the first characterized phlorin complex of a heavy transition metal. The dual reactivity of Rh(OEP)(PEt3) is proposed to arise from thermal excitation of the unpaired electron from the porphyrin-based HOMO onto the metal-based LUMO (dσ*Rh-P). Unlike the other reported 1:1 adducts of RhII(por) species with σ-basic ligands, Rh(OEP)(PEt3) is remarkably stable toward disproportionation to RhI and RhIII. To understand the origin of this stability, the affinity of RhIII(OEP)+ toward PEt3 and pyridine was measured spectrophotometrically. The high binding affinity of PEt3 to Rh(OEP) is proposed as the underlying cause of the increased stability of Rh(OEP)(PEt3) toward disproportionation

Structural and Spectroscopic Characterization of a Metal−Metal Bonded Ruthenium Porphyrin Dimer Cation

Structural and Spectroscopic Characterization of a Metal−Metal Bonded Ruthenium Porphyrin Dimer Catio

Structural and Spectroscopic Characterization of a Metal−Metal Bonded Ruthenium Porphyrin Dimer Cation

Structural and Spectroscopic Characterization of a Metal−Metal Bonded Ruthenium Porphyrin Dimer Catio

5,10,15-Tris(<i>o-</i>aminophenyl) Corrole (TAPC) as a Versatile Synthon for the Preparation of Corrole-Based Hemoprotein Analogs

The atropisomers of 5,10,15-tris(o-aminophenyl) corrole (αβα, ααβ, and ααα) are metastable at room temperature as a result of the low rotational barrier of the o-aminophenyl pickets adjacent to the bipyrrole moiety. Atropisomer enrichment of TAPC was required for the preparation of picket fence, triazacyclononane-capped, and trisimidazole-ααα-corroles. A racemic α2β model of cis-A2B geometry was also obtained by linking two cis anilines with a short strap and inserting an imidazole tail on the opposite face of TAPC

Structural and Spectroscopic Characterization of a Metal−Metal Bonded Ruthenium Porphyrin Dimer Cation

Structural and Spectroscopic Characterization of a Metal−Metal Bonded Ruthenium Porphyrin Dimer Catio