Heterobimetallic Nitrido Complexes of Group 8 Metalloporphyrins

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

doi:10.1021/acs.inorgchem.7b00281

Cited by 15 publications

(10 citation statements)

References 45 publications

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“…The original bridging Cl ligand is transformed to the terminal Cl ligand. The formation of the bridging nitrido ligand is consistent with short Ru–N distances (1.741(5) and 1.752(5) Å), which are similar to those of other dinuclear ruthenium μ-nitrido complexes. − The range of the Ru–N distances in the symmetric binding mode of the μ-nitrido ligand is 1.716–1.827 Å (av. 1.75 Å).…”

Section: Resultssupporting

confidence: 74%

Nitrite Reduction Cycle on a Dinuclear Ruthenium Complex Producing Ammonia

et al. 2018

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The fundamental biogeochemical cycle of nitrogen includes cytochrome c nitrite reductase, which catalyzes the reduction of nitrite ions to ammonium with eight protons and six electrons (NO + 8H + 6e → NH + 2HO). This reaction has motivated researchers to explore the reduction of nitrite. Although a number of electrochemical reductions of NO have been reported, the synthetic nitrite reduction reaction remains limited. To the best of our knowledge, formation of ammonia has not been reported. We report a three-step nitrite reduction cycle on a dinuclear ruthenium platform {(TpRu)(μ-pz)} (Tp = HB(pyrazol-1-yl)), producing ammonia. The cycle comprises conversion of a nitrito ligand to a NO ligand using 2H and e, subsequent reduction of the NO ligand to a nitrido and a HO ligand by consumption of 2H and 5e, and recovery of the parent nitrito ligand. Moreover, release of ammonia was detected.

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Section: Resultssupporting

confidence: 74%

Nitrite Reduction Cycle on a Dinuclear Ruthenium Complex Producing Ammonia

et al. 2018

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“…Our previous work has demonstrated that the electrophilic Ru(VI) nitrido complex [L OEt Ru(N)Cl 2 ] ( 1 ; L OEt – = [CpCo{P(O)(OEt) 2 } 3 ] − ) (Scheme ) can function as a two-electron oxidant for low-valent organometallic complexes through the formation of Ru–N–M bridges. − …”

Section: Introductionmentioning

confidence: 77%

Tetranuclear Ruthenium Cyclopentadienyl and Pentamethylcyclopentadienyl Complexes Containing Bridging Nitrido Ligands

et al. 2018

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Tetranuclear Ru μ-nitrido complexes have been synthesized by reactions of Ru(II) cyclopentadienyl and pentamethylcyclopentadienyl complexes with Ru(VI) terminal nitrides. Treatment of [RuCp2] (Cp = η5-C5H5) with [LOEtRuVI(N)Cl2] (LOEt – = [CpCo{P(O)(OEt)2}3]−) (1) afforded a tetranuclear RuIV 2-RuIII 2 μ-nitrido complex, [CpRu{(μ-N)RuCl2LOEt}{(μ-Cl)RuClLOEt}{(μ-NC5H4NH)RuCl2LOEt}] (2), that contains a bridging monodeprotonated cyclopent-4-ene-1,3-diimine ligand. The formation of 2 possibly involves the migratory insertion of the Ru nitride with a Ru-η1-C5H5 intermediate derived from the η5–η1 ring slippage of [RuCp2] and subsequent C–H activation of the cyclopentadienylimido ligand by another molecule of 1. Treatment of [Cp*Ru(MeCN)3](PF6) (Cp* = η5-C5Me5) with [LOEtM(N)Cl2] afforded [{Cp*Ru(μ-N)M(LOEt)}2(μ-Cl)4](PF6)2 (M = Ru (3), Os (4)). Treatment of [Cp*Ru(MeCN)3](PF6) with mer-[Ru(N)Cl3(AsPh3)2] yielded [{Cp*Ru(μ-N)RuCl(AsPh3)}2(μ-Cl)4(μ-O2PF2)](PF6) (5), which contains a bridging difluorophosphate ligand. The crystal structures of 2, 3, and 5 have been determined. The short Cp*Ru–N distances in 3 (1.777(7) Å) and 5 (1.772(7) and 1.775(7) Å) are indicative of the RuIVNRuIV bonding description.

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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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Heterobimetallic Nitrido Complexes of Group 8 Metalloporphyrins

Cited by 15 publications

References 45 publications

Nitrite Reduction Cycle on a Dinuclear Ruthenium Complex Producing Ammonia

Nitrite Reduction Cycle on a Dinuclear Ruthenium Complex Producing Ammonia

Tetranuclear Ruthenium Cyclopentadienyl and Pentamethylcyclopentadienyl Complexes Containing Bridging Nitrido Ligands

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

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