Syntheses of Acyliridium Porphyrins by Aldehydic Carbon−Hydrogen Bond Activation with Iridium(III) Porphyrin Chloride and Methyl

Abstract

Acyliridium porphyrins were synthesized by the reactions of aryl aldehydes with iridium(III) porphyrin chloride and methyl under solvent-free conditions with high yields. Selective aldehydic carbon hydrogen bond activation (CHA) was observed without any aromatic CHA in all the cases. Mechanistic investigation on the reactions with Ir(ttp)Cl(CO) suggested that (ttp)Ir cation was a likely intermediate of aldehydic CHA, whereas the CHA with Ir(ttp)Me underwent an oxidative addition or σ bond metathesis pathway. These reactions provided a facile synthesis of (arylacyl)iridium porphyrins.

A Rhodium‐Mediated Contraction of Benzene to Cyclopentadiene: Transformations of Rhodium(III) m‐Benziporphyrin

“…Initially two hypotheses were considered. [24,25] First, 13 CO-labelled rhodium complex 3-13 CO was used as the substrate.T he regular 1 HNMR and 13 CNMR spectroscopic patterns for the formation of compound 5 excluded the incorporation of a 13 Ccenter ( 13 CO) into the CHCHO fragment. [23] Alternatively, efficient activation over the course of the reaction was considered, including the bond cleavage of esters,aldehydes, or ketones added or formed in solution.…”

Strongly Phosphorescent Iridium(III)–Porphyrins – New Oxygen Indicators with Tuneable Photophysical Properties and Functionalities

“…The question arises whether Ir III –porphyrins show any kind of luminescence at room temperature. In fact, the combination of Ir III as central metal and porphyrins as ligands is relatively rare in the literature,9–13 and mainly the catalytic properties of such complexes have been studied 14–16. Recently,barely luminescent (quantum yield from 0.03 to 1.2 %) Ir III –corrols have been reported 17…”

Half‐Sandwich and Triangular‐Sandwich Supramolecular Solid State Structures of C60 with Ir(ttp)Me

“…The bond length of Ir-Me is 2.059(11) Å, a typical Ir-C single bond. 11,12 As shown in Scheme I, Ir(ttp)Me/C 60 complexes 1, 2 and 3 were easily prepared by mixing Ir(ttp)Me and C 60 in 1:1, 2:1 and 3:1 ratio, respectively in C 6 D 6 solution in air. Ir(ttp)Me was first dissolved in C 6 D 6 and then different equivalents of C 60 were added.…”