106161-22-2Relevant academic research and scientific papers
Alkylation of rhodium porphyrins using ammonium and quinolinium salts
Thompson, Samuel J.,Dong, Guangbin
supporting information, p. 3757 - 3767 (2014/08/18)
Alkylation of rhodium(III) porphyrins [RhIII(por)] was achieved under relatively mild conditions in up to 98% yields, where readily available ammonium and quinolinium salts were utilized as the alkylating agents. This transformation tolerates air and water, thus serving as a convenient method to prepare a variety of alkyl- and benzyl-RhIII(por) complexes. Preliminary mechanistic studies support an SN2-like reaction pathway involving a RhI(por) anion intermediate.
Reaction of electrochemically generated monomeric (tetraphenylporphinato)rhodium(II) with alkenes and alkynes. Formation of rhodium(III) σ-bonded complexes
Anderson,Yao,Kadish
, p. 706 - 711 (2008/10/08)
The reaction of electrochemically generated (tetraphenylporphinato)rhodium(II) with HC≡CR and H2C=CHR, where R is M-C3H7, n-C4H9, n-C5H11, or n-C6H13, was investigated by electrochemical and spectroscopic techniques. The ultimate rhodium porphyrin product was identified as (TPP)Rh(R), where TPP is the dianion of tetraphenylporphyrin and R is n-C3H7, n-C4H9, n-C5H11, or n-C6H13. An intermediate is observed in this reaction, and UV-visible, ESR, and electrochemical data are presented for this species. In addition, a complete reaction scheme consistent with all of the electrochemical, spectroelectrochemical, and spectroscopic data is presented. The unusual reactivity reported in this paper has not previously been observed in the reactions of rhodium porphyrins with alkenes or alkynes.
Electrochemical Studies of Rhodium-Carbon Bond Formation. The Reaction of Monomeric (Tetraphenylporphinato)rhodium(II) with Alkyl and Aryl Halides
Anderson, J. E.,Yao, C.-L.,Kadish, K. M.
, p. 1106 - 1111 (2007/10/02)
The reaction of electrochemically generated (TPP)Rh (where TPP is the dianion of tetraporphyrin) with 24 different alkyl or aryl halides (RX) was monitored by electrochemical and spectroelectrochemical methods. (TPP)Rh was generated by the one-electron reduction of +Cl-, where L is dimethylamine.The reduced rhodium complex reacts with alkyl halides in solution to form (TPP)Rh(R) and X-, and the synthesis of 14 different (TPP)Rh(R) complexes by this method is reported.However, no reaction between (TPP)Rh and aryl halides is observed.Relative reaction rate constants for the reaction between (TPP)Rh and the alkyl halides were evaluated as a function of both the halide, X, and the R group of the alkyl halide.In general, the dependence of the reaction rate constants on the halide followed the trend I > Br > F >/= Cl, while the dependence of the reaction rate constants on R of the straight chain isomers followed the trend CH3 > C2H5 ca.C3H7 ca.C4H9 ca.C5H11.On the basis of these results, a general discussion of the reaction mechanism for the formation of (TPP)Rh(R) from (TPP)Rh and RX is presented.
