Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 22nd May 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.



Iridium Porphyrin Complexes with μ-Nitrido, Hydroxo, Hydrosulfido and Alkynyl Ligands

Abstract

Iridium porphyrin complexes containing μ-nitrido, hydroxo, hydrosulfido, and alkynyl ligands have been synthesized and structurally characterized, and their oxidation has been studied. The alkyl-IrIII porphyrin complex [Ir(tpp)R] (tpp2- = 5,10,15,20-tetraphenylporphyrin dianion; R = C8H13; 1) was synthesized by reaction of [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) with H2tpp in refluxing monoethylene glycol. Treatment of 1 with PPh3 and [(LOEt)Ru(N)Cl2] (LOEt- = [(η5-C5H5)Co{P(O)(OEt)2}3]-) gave [Ir(tpp)(R)(PPh3)] (2) and the μ-nitrido complex [R(tpp)Ir(μ-N)RuCl2(LOEt)] (3), respectively. The cyclic voltammogram of 3 exhibited a reversible oxidation couple at 0.39 V versus Fc+/0 (Fc = ferrocene). The oxidation of 3 with [(4-BrC6H4)3N](SbCl6) resulted in Ir-C bond homolysis and formation of the chloride complex [Cl(tpp)Ir(μ-N)RuCl2(LOEt)] (4). The short Ir-N(nitrido) bond distances in 3 [1.891(6) Å] and 4 [1.831(4) Å] are indicative of multiple bond character and thus these two μ-nitrido complexes can be described by the two resonance forms: IrIII-N≡RuVI and IrV=N=RuIV. Similarly, the oxidation of 2 with [(4-BrC6H4)3N](SbCl6) yielded [Ir(tpp)Cl(PPh3)] (5). Chloride abstraction of 5 with TlPF6 in tetrahydrofuran (thf) afforded [Ir(tpp)(PPh3)(thf)](PF6) (6) that reacted with CsOH.H2O and Li2S to give the hydroxo [Ir(tpp)(OH)(PPh3)] (7) and hydrosulfido [Ir(tpp)(PPh3)(SH)] (8) complexes, respectively. Treatment of 6 with phenylacetylene in the presence of CuI and Et3N yielded the bimetallic complex [Ir(tpp)(PPh3)(μ-η1:η2-C≡CPh)(CuI)] (9), whereas the transmetallation of 6 with LiC≡CPh afforded the mononuclear alkynyl complex [Ir(tpp)(PPh3)(C≡CPh)] (10). The electrochemistry of the Ir porphyrin complexes have been studied using cyclic voltammetry. On the basis of the measured redox potentials of [Ir(tpp)(PPh3)X], the ability of X- to stabilize the IrIV state is ranked in the order: R- > PhC≡C- > Cl- ~ OH-. Oxidation of 8 and 9 with [(4-BrC6H4)3N](SbCl6) led to isolation of 5 and [Ir(tpp)(PPh3)(H2O)]+, respectively. The crystal structures of complexes 3, 4, and 7-10 have been determined.

Back to tab navigation

Supplementary files

Publication details

The article was received on 17 Jan 2019, accepted on 15 May 2019 and first published on 15 May 2019


Article type: Paper
DOI: 10.1039/C9DT00244H
Dalton Trans., 2019, Accepted Manuscript

  •   Request permissions

    Iridium Porphyrin Complexes with μ-Nitrido, Hydroxo, Hydrosulfido and Alkynyl Ligands

    S. So, W. Cheung, W. Chiu, M. de Vere-Tucker, H. H-Y. Sung, I. D. Williams and W. Leung, Dalton Trans., 2019, Accepted Manuscript , DOI: 10.1039/C9DT00244H

Search articles by author

Spotlight

Advertisements