103533-61-5

Upstream product

• 205259-72-9 rhodium(III) tetrakis(4-tolyl)porphyrin chloride 
• 74-88-4 methyl iodide 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 252868-55-6 rhodium(III)(5,10,15,20-tetratolylporphyrinato dianion)CH₂CH_2Ph 
• 80037-90-7 1,1,3,3-tetramethyl-2,3-dihydro-1H-isoindol-2-yloxoyl radical 
• 623-12-1 4-chloromethoxybenzene 
• 67-56-1 methanol 
• 1228390-55-3 sodium [5,10,15,20-tetrakistolylporphyrinato]rhodate(I) 
• 811-98-3 d⁽⁴⁾-methanol 
• 386707-36-4 Rh(5,10,15,20-tetrakistolylporphyrinato)CD₃ 
• 103562-26-1 Rh(5,10,15,20-tetrakistolylporphyrinato)(CH₂OH) 
• 103562-44-3 (5,10,15,20-tetrakis-4-tolylporphyrinato)rhodium(III) hydride 
• 1011457-31-0 rhodium(III)(5,10,15,20-tetratolylporphyrinato dianion)CH₂CH₂CN 
• 252868-57-8 rhodium(III)(5,10,15,20-tetratolylporphyrinato dianion)ⁿPr 

Downstream Products

• 301526-49-8 Rh(TTP)(CH₃)(CNpy) 
• 911206-95-6 [Rh(5,10,15,20-tetratolylporphyrinato)SiPhMeH] 
• 874299-87-3 (tert-butylformyl)(5,10,15,20-tetrakis-4-tolylporphyrinato)rhodium(III) 
• 911206-80-9 [Rh(5,10,15,20-tetratolylporphyrinato)SiEt₃] 
• 911206-93-4 [Rh(5,10,15,20-tetratolylporphyrinato)SiPhMe₂] 
• 936074-29-2 (4-dimethylaminobenzoyl)(5,10,15,20-tetrakis-4-tolylporphyrinato)rhodium(III) 
• 911206-92-3 [Rh(5,10,15,20-tetratolylporphyrinato)SiBnMe₂] 
• 911206-96-7 [Rh(5,10,15,20-tetratolylporphyrinato)SiPh₂Me] 
• 911206-91-2 [Rh(5,10,15,20-tetratolylporphyrinato)SiPh₂H] 
• 911206-94-5 [Rh(5,10,15,20-tetratolylporphyrinato)Si(OEt)3] 
• 874299-63-5 (4-formylbenzyl)(5,10,15,20-tetrakis-4-tolylporphyrinato)rhodium(III) 
• 874299-65-7 (4-formylphenyl-1,1-dimethylethyl)(5,10,15,20-tetrakis-4-tolylporphyrinato)rhodium(III) 
• 930573-98-1 rhodium(III)(5,10,15,20-tetratolylporphyrinato dianion)Bn(4-tBu) 
• 874299-61-3 (benzyl)(5,10,15,20-tetrakis-4-tolylporphyrinato)rhodium(III) 

Relevant academic research and scientific papers

Comparative study of rhodium and iridium porphyrin diaminocarbene and N-heterocyclic carbene complexes

Iridium meso-tetratolylporphyrinato (TTP) mono- and bis-diaminocarbene complexes, [Ir(TTP)[=C(NHBn)(NHR)]2-x(C≡NBn) x]BF4, where R = Bn, n-Bu and x = 1, 0, were synthesized by nucleophilic addition of amines to the bis-isocyanide complex [Ir(TTP)(C≡NBn)2]BF4. Rhodium and iridium porphyrinato N-heterocyclic carbene (NHC) complexes M(TTP)CH3(NHC), where NHC = 1,3-diethylimidazolylidene (deim) or 1-(n-butyl)-3- methylimidazolylidene (bmim), were prepared by the addition of the free NHC to M(TTP)CH3. The NHC complexes displayed two dynamic processes by variable-temperature NMR: meso-aryl-porphyrin C-C bond rotation and NHC exchange. meso-Aryl-porphyrin C-C bond rotation was exhibited by both rhodium and iridium complexes at temperatures ranging between 239 and 325 K. Coalescence data for four different complexes revealed δ? ROT values of 59 ± 2 to 63 ± 1 kJ·mol -1. These relatively low rotation barriers may result from ruffling distortions in the porphyrin core, which were observed in the molecular structures of the rhodium and iridium bmim complexes. Examination of NHC exchange with rhodium complexes by NMR line-shape analyses revealed rate constants of 3.72 ± 0.04 to 32 ± 6 s-1 for deim displacement by bmim (forward reaction) and 2.7 ± 0.4 to 18 ± 2 s-1 for bmim displacement by deim (reverse reaction) at temperatures between 282 and 295 K, corresponding to δf? of 65.2 ± 0.6 kJ·mol-1 and δr ? of 66.2 ± 0.5 kJ·mol-1, respectively. Rates of NHC exchange with iridium were far slower, with first-order dissociation rate constants of (1.75 ± 0.04) × 10 -4 s-1 for the forward reaction and (1.2 ± 0.1) × 10-4 s-1 for the reverse reaction at 297.1 K. These rate constants correspond to δ? values of 94.2 ± 0.6 and 95.2 ± 0.2 kJ·mol-1 for the forward and reverse reactions, respectively. Equilibrium constants for the exchange reactions were 1.6 ± 0.2 with rhodium and 1.56 ± 0.04 with iridium, favoring the bmim complex in both cases, and the log(K) values for NHC binding to M(TTP)CH3 were 4.5 ± 0.3 (M = Rh) and 5.4 ± 0.5 (M = Ir), as determined by spectrophotometric titrations at 23°C. The molecular structures also featured unusually long metal-Ccarbene bonds for the bmim complexes (Rh-CNHC: 2.255(3) A and Ir-C NHC: 2.194(4) A).

Alkylation of Rhodium Porphyrin Complexes with Primary Alcohols under Basic Conditions

Primary alcohols were successfully utilized as the alkylating reagents to conveniently access rhodium porphyrin alkyl complexes in up to 91% yields under basic conditions. Mechanistic investigations suggest two possible pathways for the C-O bond cleavage: (1) nucleophilic substitution with rhodium(I) porphyrin anion and (2) a borrowing hydrogen pathway via rhodium(III) porphyrin hydride.

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

Aryl carbon-chlorine (Ar-Cl) and aryl carbon-fluorine (Ar-F) bond cleavages by rhodium porphyrins

Aryl carbon-chlorine (Ar-Cl) bond cleavage has been achieved with rhodium(III) tetrakis-4-tolylporphyrin chloride (Rh(ttp)Cl) to give Rh(ttp)Ar. For 4-chlorofluorobenzene, the aryl carbon-fluorine (Ar-F) bond cleavage competes with the Ar-Cl bond cleavage. Mechanistic investigations show that the Ar-Cl bond cleavage goes through metalloradical ipso-substitution mechanism, while the Ar-F bond cleavage goes through nucleophilic aromatic substitution. The selectivity of the Ar-F or Ar-Cl bond cleavage can be controlled by tuning the temperature and substrate concentration.

Carbon-nitrogen bond activation of amines by rhodium(III) porphyrin complexes

Carbon-nitrogen bond activation of amines by rhodium porphyrin chloride has been achieved to give rhodium porphyrin alkyl complexes. Rhodium porphyrin hydride and rhodium porphyrin dimer were proposed as the intermediates in cleaving the C-N bond.

Reactivity studies of rhodium(III) porphyrins with methanol in alkaline media

Rh(ttp)Cl (la) (ttp = 5,10,15,20-tetrakistolylporphyrinato dianion) was found to react with methanol at a high temperature of 150 °C in the presence of inorganic bases to give a high yield of Rh(ttp)CH3 (2a), up to 87%. Rh(ttp)H (1d) is suggested to be th

Reactions of nitroxides with metalloporphyrin alkyls bearing beta hydrogens: Aliphatic carbon-carbon bond activation by metal centered radicals

Nitroxide-induced beta-hydrogen atom abstraction and beta-elimination of rhodium porphyrin alkyls have been observed. Rhodium(II) porphyrin radical were proposed intermediates to form first and subsequently reacted via aliphatic carbon-carbon bond activation with alkyl substituted nitroxides to yield rhodium porphyrin alkyl complexes.

Syntheses of acyl rhodium porphyrins by aldehydic carbon-hydrogen bond activation with Rh(III) porphyrin chloride and methyl

Rhodium(III) porphyrin chloride reacted with aryl aldehydes in solvent-free conditions to give acyl rhodium porphyrins. Selective aldehydic without any aromatic carbon-hydrogen bond activation (CHA) was observed. At lower temperature, reduction and side products were found. Alkanals reacted poorly. On the other hand, Rh(III) porphyrin methyl reacted more cleanly with both aryl and alkyl aldehydes. These reactions provided a facile, convenient synthesis of acyl rhodium porphyrins. These activations are unique CHA by high-valent Rh(III) species. Preliminary mechanistic experiments suggested that the rhodium(III) porphyrin chloride initially formed a cationic rhodium(III) porphyrin via chloride dissociation and then underwent oxidative addition or heterolysis to yield the product. On the other hand, rhodium(III) porphyrin methyl underwent either oxidative addition or σ bond metathesis.

Nonradical trapping pathway for reactions of nitroxides with rhodium porphyrin alkyls bearing β-hydrogens and subsequent carbon-carbon bond activation

A novel nitroxide-induced hydrogen atom abstraction and β-elimination of rhodium porphyrin alkyls was observed. The subsequent carbon-carbon bond activation of methyl-substituted nitroxides by the rhodium(II) porphyrin radical yielded rhodium porphyrin methyl complexes. A nonradical trapping pathway for reactions of 2,2,6,6-tetramethylpiperidinoxy (TEMPO) nitroxide with rhodium porphyrin alkyls was identified.