43145-39-7

Upstream product

• 65024-11-5 chloro(2,3,7,8,12,13,17,18-octaethylporphyrinato)chromium(III) 
• 84206-81-5 nitridomanganese(V) meso-tetrakis(4-methylphenyl)porphyrinate 
• 80584-26-5 (5,10,15,20-tetra-p-tolylporphyrinato)oxochromium(IV) 

Downstream Products

• 84174-28-7 nitrido{5,10,15,20-tetrakis(4-methylphenyl)porphinato}chromium(V) 
• 28265-17-0 (chloro)(2,3,7,8,12,13,17,18-octaethylporphyrinato)manganese(III) 
• 65024-11-5 chloro(2,3,7,8,12,13,17,18-octaethylporphyrinato)chromium(III) 
• 80593-65-3 μ-oxo-bis(5,10,15,20-tetraphenylporphyrinato)chromium(III) 
• 94890-18-3 (5,10,15,20-tetra-p-tolylporphyrinato)chromium(II) 
• 91172-68-8 [5,10,15,20-tetrakis(4-methylphenyl)porphyrinato](trimethylphosphit)chromium(III) hexafluorophosphate 
• 80584-27-6 oxo(5,10,15,20-tetra-p-tolylporphyrinato)chromium(IV)-benzene( 1/1) 
• 80584-26-5 (5,10,15,20-tetra-p-tolylporphyrinato)oxochromium(IV) 

Relevant academic research and scientific papers

Stereoelectronic Aspects of Inter-Metal Nitrogen Atom Transfer Reactions between Nitridomanganese(V) and Chromium(III) Porphyrins

Reactions of nitridomanganese(V) porphyrins with chromium(III) porphyrins resulted in the irreversible formation of nitridochromium(V) porphyrins and manganese(III) porphyrins. The progress of these reactions has been followed spectrophotometrically, electrochemically, and spectroscopically by EPR. Kinetic analysis of the spectrophotometric data obtained during these reactions for a variety of substituted porphyrins showed the reactions to be first order in each of the reactants. Rate constants were dependent upon the electronic and steric effects of the porphyrin substituent, upon the identity of the anion bound to the chromium(III) reactant, and upon the solvent dielectric constant. We propose that the mechanism of these nitrogen atom transfer reactions involves the nucleophilic attack of the nitridomanganese porphyrin donor on the cationic chromium(III) porphyrin acceptor facilitating a net, two-electron redox process mediated by a heterobimetallic μ-nitrido intermediate. This report represents the first systematic study of the stereoelectronic effects involved in the complete, inter-metal nitrogen atom transfer between two metalloporphyrins.

Synthesis, characterization, and reactivity of novel organochromium(III) porphyrin complexes

The preparations of the organometallic porphyrin complexes (TTP)CrR (TTP is the dianion of meso-tetra-p-tolylporphyrin; R is C6H5, C6H4tBu-p, or CH2SiMe3) are described. The new

Oxygen atom transfer reactions of chromium porphyrins: An electronic rationale for Oxo transfer versus μ-Oxo product formation

Treatment of (meso-tetra-p-tolylporphyrinato)chromium(IV) oxide, (TTP)Cr=O, with (octaethylporphyrinato)- chromium(III) chloride, (OEP)Cr-Cl, in benzene results in the reversible exchange of axial ligands to form (TTP)Cr-Cl and (OEP)Cr=O. The net result is a formal one-electron redox process. This occurs with a second-order rate constant of 0.14 ± 0.01 M-1 s-1 to form an equilibrium mixture with K = 2.7 ± 0.1 at 30°C (ΔH? = 15.4 ± 0.7 kcal/mol, ΔS? = -12 ± 2 cal/(mol·K), ΔH° = -2.0 ± 0.4 kcal/mol, and ΔS° = -4.6 ± 1.2 cal/(mol·K)). Use of pivalate in place of chloride on the Cr(III) complex causes no significant change in the rate of this one-electron redox process. The sterically protected Baldwin's C2-capped (porphyrinato)chromium(III) complex, (CAP)Cr-Cl, also undergoes oxygen atom transfer with (OEP)Cr=O at a similar rate. In addition, excess chloride inhibits the rate of oxygen transfer with chlorochromium(III) complexes. These results support an inner-sphere mechanism involving a μ-oxo intermediate which is formed after an initial ligand (chloride or pivalate) dissociation from the chromium(UI) reductant.