342790-12-9

Upstream product

• 85990-32-5 (5,10,15,20-tetra(2,4,6-trimethylphenyl)porphyrinato)rhodium(III) iodide 
• 75-03-6 ethyl iodide 
• 121393-39-3 5,10,15,20-tetra(2,4,6-trimethylphenyl)porphyrinate rhodium(II) 
• 5558-78-1 2-phenyl-pentanenitrile 
• 607-01-2 ethyl-diphenyl-phosphane 
• 111-43-3 Dipropyl ether 
• 1234321-53-9 1,1,3,3-tetrabutylisoindolin-2-oxyl 
• 22104-03-6 1,1,3,3-tetraethyl-1,3-dihydroisoindol-2-yloxyl 
• 769-68-6 2-phenylbutanenitrile 

Relevant academic research and scientific papers

Room-temperature selective aliphatic carbon-carbon bond activation and functionalization of ethers by rhodium(II) porphyrin

Selective aliphatic carbon(α)-carbon(β) bond activation of ethers by (5,10,15,20-tetramesitylporphyrinato)rhodium(II) (Rh(tmp) (1)) was achieved at room temperature to yield corresponding rhodium porphyrin alkyls and the functionalized esters. Rh(tmp)OH was the proposed intermediate responsible for cleaving the C(α)-C(β) bond. The reaction is general for both straight- and branch-chain ethers.

Ligand-enhanced aliphatic carbon-carbon bond activation of nitroxides by rhodium(II) porphyrin

Rh(tmp) underwent Ph3P-enhanced aliphatic carbon-carbon bond activation with various nitroxides. (Ph3P)Rh(tmp), rapidly formed from Rh(tmp) and Ph3P, enhanced the rate, selectivity, and yield in comparison to Rh(tmp). From kinetic studies, the rate of reaction showed a first-order dependence on both Rh(tmp) and TEMPO (TEMPO = 2,2,6,6- tetramethylpiperidine-1-oxyl) and saturation kinetics on Ph3P. The rate enhancement of (Ph3P)Rh(tmp) over Rh(tmp) was estimated to be about 11 at 70 °C.

Base-promoted, selective aliphatic carbon-carbon bond cleavage of ethers by rhodium(III) porphyrin complexes

Summary: Base-promoted, selective aliphatic carbon(α)carbon(β) bond activation (CCA) of ethers by (5,10,15,20tetramesitylporphyrinato) rhodium(III) iodide was achieved.

Metalloradical activations of aliphatic carbon-carbon bonds of nitriles: Scope and mechanism

The C(sp3)-C(sp3) bonds of a series of α-alkylacetonitriles, 2-silylacetonitriles and 2-alkylbenzonitriles, have been activated by Rh(tmp) using Ph3P as the optimized promoter ligand at 130°C. Selective aliphatic-aliphatic carbon-carbon bond activation (CCA) occurred for α-alkylacetonitriles and 2-alkylbenzonitriles without aromatic-aliphatic or aromatic-cyanide bond activation. Competitive activations of C-Si and C-C bonds were observed for 2-silylacetonitriles. The yields of Rh(tmp) alkyls were affected by bond energy and steric hindrance of the nitriles. Kinetic studies for the carbon-carbon bond activation (CCA) of tBuCN at 130°C revealed the rate law: rate = k′K 1[Rh(tmp)]m[Ph3P]n + k 3K2(K1[Ph3P])/(1 + K 1[Ph3P])[Rh(tmp)][tBuCN]. The CCA is proposed to occur at the coordinated tBuCN with Rh(tmp) in a 1:1 ratio in the transition state.

Activation of aliphatic carbon-carbon bonds of esters and amides by rhodium(II) porphyrin

Aliphatic carbon-carbon bonds of esters and amides were activated successfully with rhodium(II) porphyrin radical to give rhodium(III) porphyrin alkyls in moderate yields.

Activation of unstrained aliphatic carbon-carbon bonds by a transition metal complex

The activation of unstrained aliphatic carbon-carbon bonds by a transition metal complex was discussed. The intermolecular activation of aliphatic carbon-carbon bonds by transition metal complexes were found to be demonstrated in the reaction of nitroxides with a rhodium(II) porphyrin radical. The analysis showed that the methyl group in the nitroxide was cleaved to give Rh(tmp)Me.