874299-61-3Relevant articles and documents
Metalloradical-catalyzed rearrangement of cycloheptatrienyl to benzyl
Chan, Yun Wai,Chan, Kin Shing
, p. 4802 - 4804 (2011)
Rh(ttp)(C7H7) rearranged to give Rh(ttp)(CH 2Ph) quantitatively at 120°C in 12 d (ttp = 5,10,15,20- tetratolylporphyrinato dianion). This process is 1010 faster than for the organic analogue. Mechanistic investi
Alkyl Carbon-Oxygen Bond Cleavage of Aryl Alkyl Ethers by Iridium-Porphyrin and Rhodium-Porphyrin Complexes in Alkaline Media
Chen, Chen,Chan, Kin Shing
, p. 3456 - 3464 (2017/10/03)
Alkyl C-O bond cleavage in aryl alkyl ethers was achieved with Rh(ttp)Cl (1a; ttp = 5,10,15,20-tetrakis(p-tolyl)porphyrinato dianion) together with competitive alkyl C-H bond activation in alkaline media. In contrast, selective alkyl C-O bond cleavage occurred with the iridium-porphyrin Ir(ttp)(CO)Cl (1b)/KOH. Mechanistic investigations indicate the coexistence of MI(ttp)- and M2II(ttp)2 (M = Rh, Ir) under basic conditions. With a weaker Rh(ttp)-Rh(ttp) bond, RhII(ttp)· metalloradical exists in an appreciable amount to cleave the alkyl C-H bond, competing with the alkyl C-O bond cleavage via RhI(ttp)-. In contrast, the more nucleophilic IrI(ttp)- cleaves the alkyl C-O bond exclusively.
K2CO3-promoted consecutive carbon-hydrogen and carbon-carbon bond activation of Cycloheptane with rhodium(III) porphyrin complexes: Formation of rhodium porphyrin cycloheptyl and benzyl
Chan, Kin Shing,Chan, Yun Wai
, p. 3702 - 3708 (2014/08/18)
K2CO3-promoted carbon-hydrogen and carbon-carbon bond activations of cycloheptane are achieved with rhodium(III) tetrakis(4-tolyl) porphyrin chloride (Rh(ttp)Cl) at 120 °C to give Rh(ttp) cycloheptyl and benzyl complexes. On the basis of mechanistic studies, Rh(ttp)Cl first reacts by ligand substitution to give Rh(ttp)OH, which then undergoes reductive elimination to give RhII2(ttp)2. The metalloradical RhII(ttp), formed via dissociation of Rh II2(ttp)2, activates the CH bond of cycloheptane to form Rh(ttp)(cycloheptyl) and Rh(ttp)H. Rh(ttp)(cycloheptyl) slowly yields Rh(ttp)(cycloheptatrieneyl) by successive β-hydride elimination to olefins and Rh(ttp)H. K2CO3 promoted the dehydrogenation of Rh(ttp)H to give RhII2(ttp)2 and H2. Both Rh(ttp)H and RhII2(ttp) 2 activate the cycloheptatriene to give Rh(ttp)(cycloheptatrienyl), which further undergoes a RhII(ttp)-catalyzed skeletal rearrangement to form Rh(ttp)Bn with rate enhancement much faster than that of the analogous organic isomerization of cycloheptatriene to toluene.