A 1-Norbornene Adduct of a Transition Metal and an Electrochemical Study of the Bridgehead Olefin Complex

Jones, Gavin D.

doi:10.1021/om0503388

Cited by 8 publications

(7 citation statements)

References 46 publications

(70 reference statements)

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“…The Ni−CF 3 bond length of 1.971(3) Å in complex 15 is considerably longer than that found for 13 (1.9312(14) Å), perhaps due to the increased sterics at the metal center for a compound containing two CF 3 groups. Since the formulation of complex 15 is strikingly similar to those of the known nonfluorinated analogues (dippe)Ni(CH 3 ) 2 ( 16 ) , and (dtbpe)NiMe 2 ( 17 ; dtbpe = 1,2-bis(di- tert -butylphosphino)ethane), crystals of 16 were grown to compare the solid-state structures. Crystals were obtained by cooling a pentane solution of 16 , and the ORTEP diagram is shown in Figure (bottom).…”

Section: Resultsmentioning

confidence: 99%

Exploring Trifluoromethylation Reactions at Nickel: A Structural and Reactivity Study

et al. 2008

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A variety of nickel(aryl)(CF 3 ) complexes supported by a chelating bisphosphine were successfully prepared in order to investigate the possibility of reductive elimination of Ar-CF 3 . The first structural comparison of a Ni-CF 3 complex with a Ni-CH 3 complex is also presented. All of the new nickel(aryl)(CF 3 ) complexes were thermally stable and did not produce Ar-CF 3 under thermal conditions. Additives had very little effect on the reductive eliminations, although water was found to afford product in 22% yield.

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Section: Resultsmentioning

confidence: 99%

Exploring Trifluoromethylation Reactions at Nickel: A Structural and Reactivity Study

et al. 2008

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“…A plethora of such π-bound ethylene complexes have been reported . There are also few exceptions of metallacyclopropane complexes based on late transition metals − in which the olefin moiety usually features a weak C–C π-bond due to electron-withdrawing substituents or a strained conformation . A knowledge gap addressed herein is late-transition-metal– bis -cyclopropane complex, which features two ethylene units.…”

Section: Introductionmentioning

confidence: 96%

A Planar Nickelaspiropentane Complex with Magnesium-Based Metalloligands: Synthesis, Structure, and Synergistic Dihydrogen Activation

et al. 2022

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The nature of transition-metal–olefin bonding has been explained by the Dewar–Chatt–Duncanson model within a continuum of two extremes, namely, a π-complex and a metallacyclopropane. The textbook rule suggests that a low-spin late-transition-metal–ethylene complex more likely forms a π-complex rather than a metallacyclopropane. Herein, we report a low-spin late-transition-metal–bis-ethylene complex forming an unprecedented planar metalla-bis-cyclopropane structure with magnesium-based metalloligands. Treatment of LMgEt (L = [(DippNCMe)2CH]−, Dipp = 2,6- i Pr2C6H3) with Ni(cod)2 (cod = 1,5-cyclooctadiene) formed the heterotrimetallic complex (LMg)2Ni(C2H4)2, which features a linear Mg–Ni–Mg linkage and a planar coordination geometry at the nickel center. Both structural features and computational studies strongly supported the Ni(C2H4)2 moiety as a nickelaspiropentane. The exposure of (LMg)2Ni(C2H4)2 to 1 bar H2 at room temperature produced a four-hydride-bridged complex (LMg)2Ni(μ-H)4. The profile of H2 activation was elucidated by density functional theory calculations, which indicated a novel Mg/Ni cooperative activation mechanism with no oxidation occurring at the metal center, differing from the prevailing mono-metal-based redox mechanism. Moreover, the heterotrimetallic complex (LMg)2Ni(C2H4)2 catalyzed the hydrogenation of a wide range of unsaturated substrates under mild conditions.

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“…Barton and coworker8d obtained nortricyclene via generation and rearrangement of 1‐norbornene. Szeimies and coworkers8e trapped 1‐norbornene through rearrangement of bicyclo[1.1.1]pentyl carbenes with isobenzofuran and it was trapped by complexing with nickel through β‐hydride elimination 8f. However, even with these advances, strong and convincing evidence for the existence of bridgehead CC bond in bicyclo[2.2.1]heptene system is still lacking.…”

Section: Methodsmentioning

confidence: 99%

Bridgehead Substitution via Putative Norborn‐1‐en‐3‐ones: Application in the Synthesis of Complex Molecules

Khan

Budanur²,

Sudheer³

2015

Chemistry A European J

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The base-mediated formation of a bridgehead double bond in a bicyclo[2.2.1]heptane system (anit-Bredt molecules) is described. The synthesis of exocyclic norbornyl enones by Wittig reaction of α-diketones is reported. These enones and their Michael adducts are used as substrates for the generation of transient bridgehead enones and their trapping with MeOH and H2 O. Bridgehead alcohols are easily synthesized from norbornyl enones and are exploited for the diversity oriented synthesis of frameworks of natural and unnatural products.

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A 1-Norbornene Adduct of a Transition Metal and an Electrochemical Study of the Bridgehead Olefin Complex

Cited by 8 publications

References 46 publications

Exploring Trifluoromethylation Reactions at Nickel: A Structural and Reactivity Study

Exploring Trifluoromethylation Reactions at Nickel: A Structural and Reactivity Study

A Planar Nickelaspiropentane Complex with Magnesium-Based Metalloligands: Synthesis, Structure, and Synergistic Dihydrogen Activation

Bridgehead Substitution via Putative Norborn‐1‐en‐3‐ones: Application in the Synthesis of Complex Molecules

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