915085-31-3

Upstream product

• 121393-39-3 5,10,15,20-tetra(2,4,6-trimethylphenyl)porphyrinate rhodium(II) 
• 6372-41-4 n-butyl-diphenylphosphane 
• 110-86-1 pyridine 
• 2769-64-4 n-butyl isonitrile 
• 693-65-2 dipentyl ether 
• 85990-32-5 (5,10,15,20-tetra(2,4,6-trimethylphenyl)porphyrinato)rhodium(III) iodide 
• 1234321-53-9 1,1,3,3-tetrabutylisoindolin-2-oxyl 
• 603-35-0 triphenylphosphine 
• 109-65-9 1-bromo-butane 
• 161407-97-2 (5,10,15,20-tetramesitylporphyrinato)rhodium(III) chloride 

Relevant academic research and scientific papers

Facile Aerobic Alkylation of Rhodium Porphyrins with Alkyl Halides

Alkylation of rhodium porphyrins was achieved in moderate to high yields in the presence of air and water. With this facile alkylation method, various alkyl RhIII(por) species, including those with tertiary alkyl, were synthesized. Mechanistic

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.

Mechanistic studies of Si-CN and C-NC bond activation of silylnitriles and alkyl isonitriles by rhodium porphyrin radical: Novel cyanide transfer

The Si-CN and C-NC bonds of silylnitriles and alkyl isonitriles were activated by (tetramesitylpor-phyrinato)rhodium(II), Rh(tmp), to give rhodium porphyrin silyls or alkyls and rhodium porphyrin cyanide, respectively. Pyridine and triphenylphosphine promoted the rates and yields of the reactions with silylnitriles, but inhibited the rates and yields of the reactions with isonitriles. The reaction of Rh(tmp) with Me3SiCN exhibited second-order kinetics (rate = kobs[Rh(tmp)][Me3SiCN]) at a sufficiently high concentration of pyridine. The reaction with BuNC showed fourth-order kinetics, second-order in each of the reactants; rate = k obs[Rh(tmp)]2[BuNC]2. A novel cyanide transfer rate-determining step was proposed to account for the reaction mechanism.