Photodissociation of cyclopentadienyliron(II) arene cations: detection and characterization of reactive intermediates by means of time-resolved laser spectroscopy

Chrisope, Douglas R.; Park, Kyung Mi; Schuster, Gary B.

doi:10.1021/ja00198a033

Cited by 47 publications

(12 citation statements)

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“…A third possibility was to exploit the significant counterion assistance observed in the photodearylation reactions of [CpFe(arene)] + complexes. 3b,3e, It was observed that nucleophilic ions substantially enhanced the quantum yield for arene displacement in dichloromethane solution . Extending this chemistry to osmium did show that bromide ion significantly increases the quantum yield for reaction 1, but side reactions of an unknown nature along with difficulties in removing the bromide made it impossible to exploit this effect synthetically. , …”

Section: Resultsmentioning

confidence: 99%

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Preparation and Reactions of [CpOs(CH₃CN)₃]⁺. A Useful Synthetic Intermediate for the Preparation of CpOsL₃ Compounds

et al. 1997

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A photochemical synthesis of [CpOs(CH3CN)3]+ is reported (Cp = η5-cyclopentadienyl). Photolysis of [CpOs(Bz)]+ (Bz = η6-benzene) in acetonitrile solution gives [CpOs(CH3CN)3]+, but only 30% conversion is achieved before significant photochemically induced decomposition of [CpOs(CH3CN)3]+ occurs. Photolysis of acetonitrile solutions of [CpOs(Bz)]+ that contain biphenyl eliminates this side reaction and allows the high-yield preparation of [CpOs(CH3CN)3]+. Quantum yields for the photodearylation reaction are identical in the presence or absence of biphenyl, suggesting that biphenyl acts as a passive filter, slowing the photochemical decomposition of [CpOs(CH3CN)3]+. [CpOs(CH3CN)3]+ reacts with arenes, CO, and polypyrazolylborate ligands, providing a high-yield route to CpOsL3 compounds under mild conditions. Compounds that were synthesized and fully characterized include [CpOs(η6-anthracene)]PF6, [CpOs(η6-rubrene)]PF6, CpOs(BPz4) (BPz4 - = tetrakis(1-pyrazolyl)borate), CpOs(HBPz3) (HBPz3 - = hydrotris(1-pyrazolyl)borate), [CpOs(CH3CN)2CO]PF6, and CpOs(CO)2Br. 1H NMR evidence for an additional species ([(CpOs)(CpOs(CH3CN))(μ-η6,η4-anth)]2+) that contains an η6 and an η4 CpOs+ group is presented. Intriguing differences between the reactivity of [CpOs(CH3CN)3]+ and [CpRu(CH3CN)3]+ with rubrene are observed, with the osmium complex showing a remarkable kinetic preference for the naphthacene backbone relative to the pendant phenyl rings.

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Section: Resultsmentioning

confidence: 99%

“…Found: C, 39.16; H, 2.56. 1 H NMR (200 MHz, d 6 -acetone): 5.43 (s, Cp, 5H), 6.62 (d of d, H 2,3 , 2H, J vic = 4.2 Hz, J allylic = 2.1 Hz), 7.41 (d of d, H , , 2H, J vic = 6.9 Hz, J allylic = 3.0 Hz), 7.66 (d of d, H 1,4 , 2H, J vic = 4.2 Hz, J allylic = 2.1 Hz), 7.84 (d of d, H , , 2H, J vic = 6.9 Hz, J allylic = 3.0 Hz), 8.37 (s, H , , 2H).…”

Section: Methodsmentioning

confidence: 99%

Preparation and Reactions of [CpOs(CH₃CN)₃]⁺. A Useful Synthetic Intermediate for the Preparation of CpOsL₃ Compounds

et al. 1997

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“…10a. This is number of organic species to be expected according to literature reports [9,10]. Thus, the photolysis of FP in aprotic solvents should yield two organic-soluble products according to the (c) following photoreaction:…”

Section: Size-exclusion Chromatography (Sec) Results For Initiator Phmentioning

confidence: 83%

“…Firstly, an anion exchange would change the reactivity of the FP-type complexes [9], since not only the efficiency of dearylation would be different but also the nucleophilicity of the counterion would be lower. Meier and Zweifel [16] reported that in cationic polymerization of epoxides photoinitiated with iron arene complexes polymerization rates decreased in the order of increasing nucleophilicity of the anions: SbF…”

Section: Blends Of Ferrocenium and Iodonium Or Sulfonium Salts (Fp/iamentioning

confidence: 99%

Cationic polymerization using mixed cationic photoinitiator systems

Kostanski

Kim

MacGregor

et al. 2007

Designed Monomers and Polymers

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Abstract-Photoinitiated cationic polymerization is useful wherever the lack of oxygen inhibition, low shrinkage and formation of polymers with good adhesion properties are essential. Rates and conversions for cationic polymerizations of epoxycyclohexylmethyl-epoxycyclohexane carboxylate (ECHC) with various cationic photoinitiators and their blends were compared. Glass-transition temperatures of polymers were determined by dynamic mechanical analysis. When photopolymerizations of ECHC with initiator blends were compared with single-initiator systems, strong synergies leading to high polymerization rates and conversions were discovered for blends of diaryliodonium hexafluoroantimonate (IA) with tolylcumyliodonium tetrakis(pentafluorophenyl)borate (IB), and cumenecyclopentadienyliron(II) hexafluorophosphate with IA and IB. Mechanisms responsible for the discovered synergies are proposed.

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“…For [CpFe-(arene)]+complexes, the only significant ion-pairing dependence was observed either in the lower dielectric methylene chloride22•24 or in mixtures of methylene chloride and nitrile solvents. 25 Further studies that address these mechanistic issues are planned.…”

Section: Cpos(chjcn)* Rubrenementioning

confidence: 99%

Ion pairing effects in the photochemistry of the cyclopentadienyl(.eta.6-benzene)osmium(II) cation. Synthesis and reactions of a synthetically useful intermediate: the cyclopentadienyltris(acetonitrile)osmium(II) cation

1993

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Photodissociation of cyclopentadienyliron(II) arene cations: detection and characterization of reactive intermediates by means of time-resolved laser spectroscopy

Cited by 47 publications

References 0 publications

Preparation and Reactions of [CpOs(CH₃CN)₃]⁺. A Useful Synthetic Intermediate for the Preparation of CpOsL₃ Compounds

Preparation and Reactions of [CpOs(CH₃CN)₃]⁺. A Useful Synthetic Intermediate for the Preparation of CpOsL₃ Compounds

Cationic polymerization using mixed cationic photoinitiator systems

Ion pairing effects in the photochemistry of the cyclopentadienyl(.eta.6-benzene)osmium(II) cation. Synthesis and reactions of a synthetically useful intermediate: the cyclopentadienyltris(acetonitrile)osmium(II) cation

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Photodissociation of cyclopentadienyliron(II) arene cations: detection and characterization of reactive intermediates by means of time-resolved laser spectroscopy

Cited by 47 publications

References 0 publications

Preparation and Reactions of [CpOs(CH3CN)3]+. A Useful Synthetic Intermediate for the Preparation of CpOsL3 Compounds

Preparation and Reactions of [CpOs(CH3CN)3]+. A Useful Synthetic Intermediate for the Preparation of CpOsL3 Compounds

Cationic polymerization using mixed cationic photoinitiator systems

Ion pairing effects in the photochemistry of the cyclopentadienyl(.eta.6-benzene)osmium(II) cation. Synthesis and reactions of a synthetically useful intermediate: the cyclopentadienyltris(acetonitrile)osmium(II) cation

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Preparation and Reactions of [CpOs(CH₃CN)₃]⁺. A Useful Synthetic Intermediate for the Preparation of CpOsL₃ Compounds

Preparation and Reactions of [CpOs(CH₃CN)₃]⁺. A Useful Synthetic Intermediate for the Preparation of CpOsL₃ Compounds