Heterobimetallic nitrido-bridged Ru(II)NOs(VIII) and Ru(II)NOs(VI) complexes containing ruthenium porphyrins

Ruthenium porphyrins constitute an unmatched family of metalloporphyrin that exhibits extraordinary versatility in binding N-donating ligands at the axial sites. [1±5] A wide variety of ruthenium porphyrins featuring axial RuÀN bonds have been prepared, including those bearing amine, [1c, 3a,3b] amido, [3b±d,g] imido, [3a,c±e,g,j] imine, [3h, 4] methyleneamido, [3h] nitrile, [1a, 2] hydrazido, [3f] nitrosoarene, [1b, 3i] nitrosyl, [5] and dinitrogen [1d] axial ligands (Scheme 1, a±j). This makes the lack of [*] Prof.

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“…This makes the lack of isolable ruthenium porphyrins with terminal nitrido axial ligands (Scheme 1, k ) especially conspicuous 6. 7…”

Section: Methodsmentioning

confidence: 99%

Nitrido Ruthenium Porphyrins: Synthesis, Characterization, and Amination Reactions with Hydrocarbon or Silyl Enol Ethers

Leung¹,

Huang²,

Liang³

et al. 2003

Angew Chem Int Ed

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“…Another additional difference is that all ruthenium or osmium nitrosyl derivatives that have been isolated and structurally characterized are exclusively six-coordinate; no five-coordinate complexes are reported. With two notable exceptions that are discussed later, the ruthenium systems all contain RuNO moieties that can be described as nominally linear. ,,− Bond lengths and angles for these ruthenium systems can be found in Table . Comparisons of structural details for species with identical axial ligands, e.g., the hydroxo and nitrito complexes, suggest that the overall level of precision of the ruthenium structures is somewhat lower than that of the iron derivatives.…”

Section: Ruthenium and Osmium Derivativesmentioning

confidence: 99%

Solid-State Structures of Metalloporphyrin NO_xCompounds

2002

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“…Although terminal nitrido complexes of Ru and Os porphyrins are well-documented, , dinuclear Ru and Os μ-nitrido porphyrin complexes are rare . Very few heterobimetallic nitrido complexes of Ru porphyrins and phthalocyanines, e.g., [(OEP)(NO)Ru(μ-N)OsO 3 ] (OEP 2– = octaethylporphyrin dianion), ,, have been synthesized and structurally characterized.…”

Section: Introductionmentioning

confidence: 99%

Heterobimetallic Nitrido Complexes of Group 8 Metalloporphyrins

et al. 2017

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Heterobimetallic nitrido porphyrin complexes with the [(L)(por)M-N-M'(L)Cl] formula {por = 5,10,15,20-tetraphenylporphyrin (TPP) or 5,10,15,20-tetra(p-tolyl)porphyrin (TTP) dianion; L = [Co(η-CH){P(O)(OEt)}]; M = Fe, Ru, or Os; M' = Ru or Os; L = HO or pyridine} have been synthesized, and their electrochemistry has been studied. Treatment of trans-[Fe(TPP)(py)] (py = pyridine) with Ru(VI) nitride [Ru(L)(N)Cl] (1) afforded Fe/Ru μ-nitrido complex [(py)(TPP)Fe(μ-N)Ru(L)Cl] (2). Similarly, Fe/Os analogue [(py)(TPP)Fe(μ-N)Os(L)Cl] (3) was obtained from trans-[Fe(TPP)(py)] and [Os(L)(N)Cl]. However, no reaction was found between trans-[Fe(TPP)(py)] and [Re(L)(N)Cl(PPh)]. Treatment of trans-[M(TPP)(CO)(EtOH)] with 1 afforded μ-nitrido complexes [(HO)(TPP)M(μ-N)Ru(L)Cl] [M = Ru (4a) or Os (5)]. TTP analogue [(HO)(TTP)Ru(μ-N)Ru(L)Cl] (4b) was prepared similarly from trans-[Ru(TTP)(CO)(EtOH)] and 1. Reaction of [(HO)(por)M(μ-N)M(L)Cl] with pyridine gave adducts [(py)(por)M(μ-N)Ru(L)Cl] [por = TTP, and M = Ru (6); por = TPP, and M = Os (7)]. The diamagnetism and short (por)M-N(nitride) distances in 2 [Fe-N, 1.683(3) Å] and 4b [Ru-N, 1.743(3) Å] are indicative of the M═N═M' bonding description. The cyclic voltammograms of the Fe/Ru (2) and Ru/Ru (4b) complexes in CHCl displayed oxidation couples at approximately +0.29 and +0.35 V versus Fc (Fc = ferrocene) that are tentatively ascribed to the oxidation of the {LRu} and {Ru(TTP)} moieties, respectively, whereas the Fe/Os (3) and Os/Ru (5) complexes exhibited Os-centered oxidation at approximately -0.06 and +0.05 V versus Fc, respectively. The crystal structures of 2 and 4b have been determined.

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Heterobimetallic nitrido-bridged Ru(II)NOs(VIII) and Ru(II)NOs(VI) complexes containing ruthenium porphyrins

Cited by 19 publications

References 36 publications

Nitrido Ruthenium Porphyrins: Synthesis, Characterization, and Amination Reactions with Hydrocarbon or Silyl Enol Ethers

Nitrido Ruthenium Porphyrins: Synthesis, Characterization, and Amination Reactions with Hydrocarbon or Silyl Enol Ethers

Solid-State Structures of Metalloporphyrin NO_xCompounds

Heterobimetallic Nitrido Complexes of Group 8 Metalloporphyrins

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Heterobimetallic nitrido-bridged Ru(II)NOs(VIII) and Ru(II)NOs(VI) complexes containing ruthenium porphyrins

Cited by 19 publications

References 36 publications

Nitrido Ruthenium Porphyrins: Synthesis, Characterization, and Amination Reactions with Hydrocarbon or Silyl Enol Ethers

Nitrido Ruthenium Porphyrins: Synthesis, Characterization, and Amination Reactions with Hydrocarbon or Silyl Enol Ethers

Solid-State Structures of Metalloporphyrin NOxCompounds

Heterobimetallic Nitrido Complexes of Group 8 Metalloporphyrins

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Solid-State Structures of Metalloporphyrin NO_xCompounds