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 Rh III (por) species, including those with tertiary alkyl, were synthesized. Mechanistic investigations suggest a parallel S N 2 via [Rh I (ttp)] − with halogen atom transfer pathway via [Rh II (ttp)] • . ■ INTRODUCTIONRhodium porphyrin alkyls ( Figure 1) play an important role in catalysis. They are precursors of [Rh II (por)] • (por = porphyrinato dianion) metalloradicals for carbon−hydrogen bond 1 and carbon−carbon single bond activation. 1d,2 Activation of these strong bonds has gained much current interest for more efficient utilization of hydrocarbons. 3 To the best of our knowledge, only primary and secondary alkyl Rh III (por) species have been reported so far. Tertiary alkyl Rh III (por) species remain unknown, which may be of great interest in investigating its role in catalysis. Hence, developing robust methods to access alkyl Rh III (por) species, especially tertiary alkyl Rh III (por) species, is important.The synthesis of rhodium porphyrin alkyls was first reported by Ogoshi in 1972 by the reaction between Rh III (oep)Cl (oep =2,3,7,8,12,13,17,18-octaethylporphyrinato dianion) and MeLi (Scheme 1a). 4 A more versatile method involves the reduction of Rh III (por)Cl by NaBH 4 to generate [Rh I (por)] − . [Rh I (por)] − then undergoes nucleophilic substitution with alkyl halides to give the corresponding rhodium porphyrin alkyls (Scheme 1b). 5 In 1986, Kadish and co-workers reported the Rh−C bond formation by the electrochemically generated monomeric species [Rh II (tpp)] • (tpp = 5,10,15,20-tetraphenylporphyrinato dianion) (Scheme 1c). 6 In 1990, Wayland discovered the formation of Rh−C bond by carbon−hydrogen bond activation of CH 4 and toluene to give Rh(por)Me and Rh(por)Bn (Scheme 1d). 1a,b The carbon−oxygen bond cleavage of methanol by Rh III (ttp)Cl (ttp =5,10,15,20-tetratolylporphyrinato dianion) in alkaline media was discovered to give a high yield of Rh III (ttp)Me and was reported by Chan in 2009 (Scheme 1e). 7 In 2010, Chan and co-workers found the formation of the Rh−C bonds by carbon−nitrogen bond activation (CNA) of amines (Scheme 1f). 8 This CNA method, further developed by the Dong group, tolerates air and water by utilizing ammonium salts as the alkylating agents (Scheme 1g). An S N 2-like reaction pathway involving a [Rh I (por)] − intermediate was proposed. 9 These reported methods are unlikely to prepare a tertiary alkyl Rh III (por) species due to the steric hindrance. Herein, we disclose a facile Figure 1. Structure of rhodium porphyrin alkyls. Scheme 1. Synthesis of Rhodium Porphyrin AlkylsArticle pubs.acs.org/Organometallics
List of Contents 1. Reaction Conditions Optimization (S2) 2. X-ray Crystallographic Data and Structure of Rh(ttp)(2-thienyl) (3b) (S3) 3. Titration Experiments (S5) 4. NMR Spectra (S11) S2 Reaction Conditions OptimizationThe general procedures described in the experimental section were followed in the optimization reactions.(1) The reaction of Co II (ttp) with thiophene:Co II (ttp) (1a; 11.3 mg, 0.0155 mmol) were added to thiophene (1000 µL, 12.5 mmol). The mixture was heated at 120 o C under air for 2 days. 1a was quantitatively recovered.Co II (ttp) (1a; 11.3 mg, 0.0155 mmol) were added to thiophene (1000 µL, 12.5 mmol). The mixture was degassed for three freeze-pump-thaw cycles, then filled with N 2 . It was then heated at 120 o C under N 2 for 4 days. Co(ttp)(2-thienyl) (3a) was obtained in trace yield with 83% recovery of 1a.Co II (ttp) (1a; 11.3 mg, 0.0155 mmol), KOH (8.7 mg, 0.155 mmol) were added to thiophene (1000 µL, 12.5 mmol). The mixture was heated at 140 o C under air for 6 days. Co(ttp)(2-thienyl) (3a) was obtained in 20% yield with 60% recovery of 1a.Co II (ttp) (1a; 11.3 mg, 0.0155 mmol), KOH (8.7 mg, 0.155 mmol) and H 2 O (28 µL, 1.55 mmol) were added to thiophene (1000 µL, 12.5 mmol). The mixture was heated at 140 o C under air for 8 days. 1a was quantitatively recovered.(2) The reaction of Rh III (ttp)Cl with thiophene:Temperature effects: Rh(ttp)Cl (1b; 11.0 mg, 0.0136 mmol), aqueous KOH (5.5 M, 24.5 µL, 0.135 mmol) were added to thiophene (1000 µL, 12.5 mmol). The mixture was heated at under air. Isolated yields of Rh(ttp)(2-thienyl) (3b) for the reaction at 180 o C for 6 h: 47%; at 200 o C for 2 h: 87%. Yields of Rh(ttp)(3-thienyl) (3c) for the reaction at 180 o C for 6 h: 4; at 200 o C for 2 h: 9%.Atmosphere effects: Rh(ttp)Cl (1b; 11.0 mg, 0.0136 mmol), aqueous KOH (5.5 M, 24.5 µL, 0.135 mmol) were added to thiophene (1000 µL, 12.5 mmol). For the reaction conducted under N 2 , the mixture was degassed for three freeze-pump-thaw cycles, then filled with N 2 .The mixture was heated at 200 o C. Rh(ttp)(2-thienyl) (3b) was obtained in 25% yield under N 2 for 4 h, and 87% yield under air. KOH loading effects: Rh(ttp)Cl (1b; 11.0 mg, 0.0136 mmol), aqueous KOH (n equiv) were added to thiophene (1000 µL, 12.5 mmol). The mixture was heated at 200 o C.
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