Synthesis, reactivity, and electrochemical characterization of [(.eta.5-C5H5)Ru(.eta.7-C7H7)](PF6)2 and [(.eta.5-C5H5)Ru(.eta.6-C7H8)](PF6)

McNair, Amy M.; Boyd, David C.; Bohling, D. A.; Gill, Thomas P.; Mann, Kent R.

doi:10.1021/ic00254a042

Cited by 16 publications

(7 citation statements)

References 2 publications

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“…Similar to the parent [(η 5 -C 5 H 5 )(η 7 -C 7 H 7 )Ru] 2+ ( 17 ), complex 4 exhibits an electrochemically quasireversible reduction. The half-wave potential at low sweep rates, where the distortions of sluggish electron transfer kinetics are minimized, is −0.83 V, which is close to that of −0.87 V for its parent.…”

Section: Resultsmentioning

confidence: 85%

“…The chemistry of these sandwich complexes has been advanced considerably in recent years, in part driven by the ring-opening polymerization (ROP) of strained ansa-derivatives to metallopolymers, in analogy with ROP of strained ansa-ferrocenes and other metallocenes . Interestingly, there is only one single example of a representative of a late transition metal, [η 5 -C 5 H 5 )Ru(η 7 -C 7 H 7 )](PF 6 ) 2 , a rather neglected result that has been cited only two times within the last 25 years. Although this compound is an air-stable 18-electron species, no further chemistry and no other derivatives are known.…”

Section: Introductionmentioning

confidence: 99%

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π-Complexes of Tropolone and Its N-Derivatives: Ambidentate [O,O]/[N,O]/[N,N]-Cycloheptatrienyl Pentamethylcyclopentadienyl Ruthenium Sandwich Complexes

et al. 2014

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Tropolone and its N-derivatives isopropylaminotropone and diisopropylaminotroponimine react with [Cp*Ru(CH 3 CN) 3 ]PF 6 as the source of the electron-rich Cp*Ru + synthon in a simple "capping reaction" to the first cyclopentadienyl/cycloheptatrienyl sandwich complexes containing two vicinal oxo or amino substituents. These heteroleptic, cationic C 5 /C 7 π-complexes, [Cp*Ru-(C 7 H 5 )O 2 H] + (4), [Cp*Ru(C 7 H 5 )O(N i Pr)H] + (5), and [Cp*Ru(C 7 H 5 )(N i Pr) 2 H] + (6), are air-stable 18-electron metallocenes without precedence. In solution, NMR spectroscopy proves the principal π-coordination of the substituted η 7 -cycloheptatrienyl ligands, whereas in the solid state a η 5 -cycloheptatrienyl coordination mode with bent oxo/imino moieties prevails, as shown by X-ray single-crystal structure analyses. Chemically, these compounds are the conjugate Brønsted acids of neutral [O,O]-, [N,O]-, or [N,N]metalloligands. Reaction with metal acetates or acetylacetonates by in situ deprotonation and complex formation gives access to trimetallic (M = Cu 2+ , 10−12) or tetrametallic (M = Fe 3+ , 13) complex cations. Their single-crystal structure analyses show square-planar or square-pyramidal (M = Cu 2+ ) or octahedral (M = Fe 3+ ) coordination motifs with peripheral, η 5 -coordinated Cp*Ru moieties. Electrochemical studies on the trorucenes 4−6 showed a likely metal-based chemically reversible (4) or irreversible one-electron reduction (5, 6) as well as an irreversible one-electron oxidation for the N-substituted compounds 5 and 6. The behavior of the heterotri-and tetrametallic complexes 10, 11, and 13 was rationalized by a combination of cyclic and square-wave voltammetry as well as the combination of chronocoulometry and linear-sweep voltammetry and by comparison with the mononuclear copper or iron tropolone and topolonimine precursors 14−16. These studies indicate that in 10 and 11 the trorucene moieties are reduced first in two coincident or slightly separated one-electron reductions with the Cu 2+ reduction at very negative potential, whereas in 13 the central Fe(III)-tris(troponolato) moiety is reduced prior to the trorucene appendices. An in vitro anticancer screening in MDA-MB-231 breast adenocarcinoma and HT-29 colon carcinoma cell lines showed enhanced antiproliferative activity for the [O,O]-coordinated iron and copper complexes.

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Section: Resultsmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

π-Complexes of Tropolone and Its N-Derivatives: Ambidentate [O,O]/[N,O]/[N,N]-Cycloheptatrienyl Pentamethylcyclopentadienyl Ruthenium Sandwich Complexes

et al. 2014

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“…The analogous aminotropone and tropolone complexes show a similar electrochemical behavior. The redox events were classified as metal‐based processes based on comparison with trorucene compounds and EPR spectroscopic measurements.…”

Section: Redox Chemistrymentioning

confidence: 99%

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

Hanft

Lichtenberg

2018

Eur J Inorg Chem

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Aminotroponiminates (ATIs) are monoanionic ligands with an N,N‐binding pocket and a rigid, planar, unsaturated, C7‐ring as a ligand backbone. Recent findings show that this ligand backbone can play an active role in coordination chemistry, redox reactions, and ligand‐centered reactivity of ATI complexes. Based on these results, ATIs have been recognized as redox‐active and cooperative ligands, which has implications for existing and potential future applications of ATI compounds in synthesis, catalysis, and materials science. The catalytic applications of ATI complexes are summarized in this Microreview, including results from the fields of hydroamination, epoxidation, cyanosilylation, ε‐caprolactone‐, olefin‐, epoxide‐, and epoxide/CO2 (co‐)polymerization as well as electron transfer catalysis. Furthermore, recent advances in the use of ATI ligands for stabilizing heavy analogs of carbon oxo compounds are showcased.

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“…Purification was achieved by recrystallization from CH 3 [15]. Generally, cycloheptatrienylium complexes are not obtained by the direct introduction of the Ch þ ligand since competing redox processes lead to other products [5,16]. However, owing to the redox stability of the Cp*Rh III fragment the reaction of [Cp*Rh(acetonitrile) 3 ] 2þ with Ch þ leads to the desired complex.…”

Section: Llct 3+mentioning

confidence: 99%

“…Last but not least, the desired complex [Cp*RhCh] 3þ should be accessible by a relatively simple synthesis. As starting material [Cp*Rh III Cl 2 ] 2 [14] is commercially available and its conversion to [Cp*Rh(acetonitrile) 3 ] 2þ [15] and finally to [Cp*RhCh] 3þ seems to be feasible in analogy to the synthesis of [CpRu II Ch] 2þ [16].…”

mentioning

confidence: 99%

Ligand-to-ligand charge transfer in [(η-C 5 Me 5 )Rh III (η-C 7 H 7 )] 3+ : absorption and emission

Kunkely¹,

Vogler²

2004

Inorganic Chemistry Communications

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Synthesis, reactivity, and electrochemical characterization of [(.eta.5-C5H5)Ru(.eta.7-C7H7)](PF6)2 and [(.eta.5-C5H5)Ru(.eta.6-C7H8)](PF6)

Cited by 16 publications

References 2 publications

π-Complexes of Tropolone and Its N-Derivatives: Ambidentate [O,O]/[N,O]/[N,N]-Cycloheptatrienyl Pentamethylcyclopentadienyl Ruthenium Sandwich Complexes

π-Complexes of Tropolone and Its N-Derivatives: Ambidentate [O,O]/[N,O]/[N,N]-Cycloheptatrienyl Pentamethylcyclopentadienyl Ruthenium Sandwich Complexes

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

Ligand-to-ligand charge transfer in [(η-C 5 Me 5 )Rh III (η-C 7 H 7 )] 3+ : absorption and emission

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