1224699-29-9

Upstream product

• 872415-81-1 (5,10,15,20-tetrakis(p-tolyl)porphyrinato)carbonyliridium(III) chloride 
• 98-86-2 acetophenone 
• 872415-82-2 Ir(ttp)CH₂COPh 
• 1319720-86-9 Ir(ttp)OH 
• 122-00-9 para-methylacetophenone 
• 13329-40-3 4-Iodoacetophenone 
• 1126-46-1 Methyl 4-chlorobenzoate 
• 99-90-1 para-bromoacetophenone 

Relevant academic research and scientific papers

Base-promoted selective aryl C-Cl cleavage by iridium(III) porphyrins via a metalloradical ipso addition-elimination mechanism

Base-promoted aryl carbon-chlorine bond (Ar-Cl) cleavage by iridium(III) porphyrin carbonyl chloride (IrIII(ttp)(CO)Cl; ttp = 5,10,15,20-tetrakis(p-tolyl)porphyrinato dianion) was achieved in the presence of K2CO3 to give iridium(III) porphyrin aryls (Ir III(ttp)Ar). Mechanistic studies revealed that K2CO 3 promotes the reduction of Ir(ttp)(CO)Cl to give the iridium(II) porphyrin dimer intermediate [IrII(ttp)2. [Ir(ttp) 2 is the source of IrII(ttp) metalloradical, which cleaves Ar-Cl to give Ir(ttp)Ar and a chlorine radical (Cl?) via radical ipso substitution in an addition-elimination pathway. Cl ? reacts with [Ir(ttp)2 to yield Ir(ttp)Cl for subsequent base-promoted reduction and Ir(ttp) for radical chain propagation. Additionally, the base-promoted Ar-Cl cleavage of chlorobenzene (PhCl) by Ir(ttp)(CO)Cl gives both Ir(ttp)Ph and 1,4-bis-iridium(III)-porphyrin benzene, IrIII(ttp)(p-C6H4)IrIII(ttp). The reactive Cl? can simultaneously react with PhCl via homolytic aromatic substitution to give 1,4-dichlorobenzene, which further undergoes double Ar-Cl cleavage to form Ir(ttp)(p-C6H4)Ir(ttp).

Base-promoted selective aryl carbon-bromine bond cleavage by Iridium(III) porphyrin for Iridium(III) porphyrin aryl synthesis: A metalloradical Ipso addition-elimination mechanism

K2CO3 was found to promote selective aryl carbon-bromine bond (Ar-Br) cleavage by a high-valent iridium(III) porphyrin carbonyl chloride (IrIII(ttp)(CO)Cl, ttp = 5,10,15,20-tetra-p- tolylporphyrinato dianion) in benzene so

Scope and mechanism of carbonyl carbon and α-carbon bond cleavage of ketones by Iridium(III) porphyrin complexes

Chemoselective carbonyl carbon and α-carbon bond activation (CCA) of ketones (RCOR) was successfully achieved with various iridium(III) tetrakis-4-tolylporphyrinato complexes Ir(ttp)X (X = (BF4)(CO), Cl(CO), and Me) to give the corresponding Ir(ttp)COR (R = Ar, Me, or Et) and Ir(ttp)R (R = Me or Et) complexes. Ir(ttp)(BF4)(CO) exhibited the highest reactivity toward CCA, as it possesses a higher Lewis acidity in catalyzing the aldol condensation of ketones to give water, which hydrolyzes the kinetic products, C-H bond activation (CHA) complexes, into the proposed Ir(ttp)OH for a subsequent CCA process. The CCA step is nonregioselective in giving both Ir(ttp)R and Ir(ttp)COR. However, Ir(ttp)R was kinetically less stable toward hydrolysis to give Ir(ttp)OH. Thus, only Ir(ttp)COR was observed as the sole CCA product.

Base-promoted selective aryl C-Br and C-I bond cleavage by iridium(III) porphyrin: Reduction of IrIII-OH to IrII for metalloradical ipso substitution of aryl-halogen bonds

Base-promoted selective aryl carbon-bromine and carbon-iodine bond (Ar-X, X = Br, I) cleavage by iridium(III) porphyrin carbonyl chloride (Ir III(ttp)(CO)Cl) was achieved in the presence of base (K 2CO3, NaOH) to give iridium(III) porphyrin aryls (Ir III(ttp)Ar). Mechanistic studies revealed that the base undergoes ligand substitution with Ir(ttp)(CO)Cl to yield an iridium(III) hydroxo species (IrIII(ttp)OH). The hydroxo ligand most likely reduces the Ir(III) center to give iridium(II) porphyrin dimer ([IrII(ttp)]2) and H2O2. In a competitive pathway, [Ir II(ttp)]2 disproportionates in the presence of base and residual water to give an iridium(III) hydride (IrIII(ttp)H) and Ir(ttp)OH. In a productive process, [Ir(ttp)]2 undergoes Ir II(ttp) metalloradical-mediated ipso substitution of Ar-X via an addition-elimination pathway to form Ir(ttp)Ar and Ir(ttp)X. Ir(ttp)X is recycled by reacting with base to regenerate [Ir(ttp)]2 for subsequent Ar-X cleavage.

Cleavage of carbonyl carbon and α-carbon bond of acetophenones by iridium(III) porphyrin complexes

Selective carbonyl carbon (C( - O)) and α-carbon (C(methyl)) bond activation of acetophenones was discovered by the high-valent, iridium(III) 5,10,15,20-tetrakis-4-tolylporphyrinato carbonyl chloride (Ir(ttp)Cl(CO)), which also acted as a Lewis acid in catalyzing the aldol condensation of acetophenones together with release of the coproduct water. Preliminary mechanistic studies suggest that both aliphatic and aromatic carbon-hydrogen bond activation products are kinetic products, which can be converted by reaction with water to iridium porphyrin hydride (Ir(ttp)H) via iridium porphyrin hydroxide (Ir(ttp)OH). Both Ir(ttp)OH and Ir(ttp)H were the possible intermediates to cleave the C( - O)-C(methyl) bond of acetophenones and to generate iridium porphyrin acyl complexes as the thermodynamic products.