Iridium porphyrin complexes with μ-nitrido, hydroxo, hydrosulfido and alkynyl ligands

So, Shiu-Chun; Cheung, Wai-Man; Chiu, Wai-Hang; Vere-Tucker, Matthew de; Sung, Herman H. Y.; Williams, Ian D.; Leung, Wa‐Hung

doi:10.1039/c9dt00244h

Cited by 9 publications

(4 citation statements)

References 61 publications

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“…Furthermore, methane hydroxylation to methanol was observed with several complexes, which implicates that these oxidants are more powerful than cytochrome P450 Cpd I [20,21]. Unprecedented reactivity of µ-nitrido diiron tetrapyrrolic complexes has initiated synthetic development of this platform involving different metals supported by various macrocyclic ligands [17,18,[22][23][24][25][26][27]. In parallel, several detailed computational studies on -nitrido bridged diiron(IV)-oxo phthalocyanine and porphyrin complexes have been reported by us and others [28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 95%

Properties and reactivity of μ-nitrido-bridged dimetal porphyrinoid complexes: how does ruthenium compare to iron?

2019

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Methane hydroxylation by metal-oxo oxidants is one of the Holy Grails in biomimetic and biotechnological chemistry. The only enzymes known to perform this reaction in Nature are ironcontaining soluble methane monooxygenase and copper-containing particulate methane monooxygenase. Furthermore, few biomimetic iron-containing oxidants have been designed that can hydroxylate methane efficiently. Recent studies reported that -nitrido bridged diiron(IV)-oxo porphyrin and phthalocyanine complexes hydroxylate methane to methanol efficiently. To find out whether the reaction rates are enhanced by replacing iron by ruthenium we performed a detailed computational study. Our work shows that the -nitrido bridged diruthenium(IV)-oxo reacts with methane via hydrogen atom abstraction barriers that are considerably lower in energy (by about 5 kcal mol -1 ) as compared to the analogous diiron(IV)-oxo complex. An analysis of the electronic structure implicates similar spin and charge distributions for the diiron(IV)-oxo and diruthenium(IV)-oxo complexes, but the strength of the O-H bond formed during the reaction is much stronger for the latter.As such a larger hydrogen atom abstraction driving force for the Ru complex than for the Fe complex is found, which should result in higher reactivity in the oxidation of methane.

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Section: Introductionmentioning

confidence: 95%

Properties and reactivity of μ-nitrido-bridged dimetal porphyrinoid complexes: how does ruthenium compare to iron?

2019

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“…Complexes I and II feature short Ir−N(nitride) distances and roughly linear Ir−N−Ru linkages (Scheme 2), indicating that there is extensive π delocalization in the Ir−N−Ru units. Thus, their bonding can be described by two resonance forms: Ir(III)−N=Ru(VI) and Ir(V)=N=Ru(IV) [14,15] …”

Section: Introductionmentioning

confidence: 99%

“…Thus, their bonding can be described by two resonance forms: Ir(III)À N=Ru(VI) and Ir(V) = N=Ru(IV). [14,15] As our continuous effort to explore the chemistry of highvalent Ir complexes bearing multiply bonded ligands, we sought to synthesize heterometallic Ir μ-nitrido complexes supported by electron-rich O-donor ligands. In this paper, we report the synthesis and structure of IrÀ NÀ Ru complexes derived from Ir(tpip) precursors.…”

Section: Introductionmentioning

confidence: 99%

Heterometallic Iridium, Rhodium and Ruthenium Nitrido Complexes Supported by Oxygen and Sulfur Donor Ligands

Chong

Cheung

et al. 2022

Eur J Inorg Chem

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Heterometallic μ‐nitrido complexes have been synthesized from organometallic complexes containing O/S‐donor ligands and a ruthenium(VI) nitride. The treatment of [Ir(tpip)(L)2] (tpip−=[N(Ph2PO)2]−; L=cyclooctene (coe) or 2,6‐dimethylphenylisocyanide (xylNC)) and [Ir{N(iPr2PS)2}(coe)] with [Ru(LOEt)(N)Cl2] (LOEt−=[Co(η5‐C5H5){P(O)(OEt)2}3]−) (1) afforded [(L)(tpip)Ir(μ‐N)Ru(LOEt)Cl2] (L=coe (2) or xylNC (3)) and [(coe){N(iPr2PS)2}Ir(μ‐N)Ru(LOEt)Cl2] (4), respectively, in which the Ir−N(nitride) bonds show double bond character. The bonding in 2–4 can be described by two resonance forms: Ir(I)−N≡Ru(VI) and Ir(III)=N=Ru(IV). The treatment of [Ph4P][Ir(CO)2Cl2] with 1 afforded (PPh4)[(CO)Cl2Ir(μ‐N)Ru(LOEt)Cl2] (5) that reacted with [Tl(SR)] to give (PPh4)[(CO)(RS)2Ir(μ‐N)Ru(LOEt)Cl2] (R=xyl (6), C6F4H (7)). The reaction of [M(acac)(CO)2)] or [Ru(acac)2(coe)2] (acac−=acetylacetonate) with 1 gave [(CO)(acac)M(μ‐N)Ru(LOEt)Cl2] [M=Ir (8), Rh (9)] or [(H2O)(acac)2Ru(μ‐N)Ru(LOEt)Cl2] (10), whereas the treatment of [Ru(acac)2(MeCN)2] with 1‐azidoadamantane (AdN3) yielded a Ru(II) tetrazene complex, [Ru(acac)2(N4Ad2)] (11).

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“…The use of the inner core of the porphyrin and analogues framework to coordinate iridium(III) was considered in different studies, affording Ir(III) porphyrinoids, which have emerged as new sources of metal catalysts [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 ], and also as complexes with distinct photoluminescent properties [ 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 ]. Alternatively, the functionalization of the porphyrin periphery with adequate metal binding groups (e.g., pyridines, terpyridines) affording assemblies with an external active metal center has also attracted a high interest from the scientific community [ 49 , 50 , 51 ].…”

Section: Introductionmentioning

confidence: 99%

New Bis-Cyclometalated Iridium(III) Complexes with β-Substituted Porphyrin-Arylbipyridine as the Ancillary Ligand: Electrochemical and Photophysical Insights

Moura

Serra

Bastos

et al. 2022

IJMS

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An efficient synthetic access to new cationic porphyrin-bipyridine iridium(III) bis-cyclometalated complexes was developed. These porphyrins bearing arylbipyridine moieties at β-pyrrolic positions coordinated with iridium(III), and the corresponding Zn(II) porphyrin complexes were spectroscopically, electrochemically, and electronically characterized. The features displayed by the new cyclometalated porphyrin-bipyridine iridium(III) complexes, namely photoinduced electron transfer process (PET), and a remarkable efficiency to generate 1O2, allowing us to envisage new challenges and opportunities for their applications in several fields, such as photo(catalysis) and photodynamic therapies.

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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.

Cited by 9 publications

References 61 publications

Properties and reactivity of μ-nitrido-bridged dimetal porphyrinoid complexes: how does ruthenium compare to iron?

Properties and reactivity of μ-nitrido-bridged dimetal porphyrinoid complexes: how does ruthenium compare to iron?

Heterometallic Iridium, Rhodium and Ruthenium Nitrido Complexes Supported by Oxygen and Sulfur Donor Ligands

New Bis-Cyclometalated Iridium(III) Complexes with β-Substituted Porphyrin-Arylbipyridine as the Ancillary Ligand: Electrochemical and Photophysical Insights

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