Transition-metal chemistry of octafluorocyclooctatetraene. Synthesis and x-ray structure of a novel five-coordinate cis-dialkylnickel complex

Hughes, Russell P.; Carl, Richard T.; Samkoff, Deborah E.; Davis, R.; Holland, Katherine D.

doi:10.1021/om00136a038

Cited by 9 publications

(8 citation statements)

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“…This architecture favors pentacoordinate geometries, which are unusual amongst predominantly square planar group 10 metallacycles. [3,[23][24][25][26][27] Depending on the presence and nature of an additional ligand, the nickelacyclobutane selectively undergoes cyclopropanation, [2+2] cycloreversion, or apparent b-hydride elimination. Experiments and computations provide insight into the mechanistic pathways.…”

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confidence: 99%

Divergent Reactivity of an Isolable Nickelacyclobutane

et al. 2021

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Nickelacyclobutanes are mostly invoked as reactive intermediates in the reaction of nickel carbenes and olefins to yield cyclopropanes. Nevertheless, early work suggested that other decomposition routes such as b-hydride elimination and even metathesis could be accessible. Herein, we report the isolation and characterization of a stable pentacoordinated nickelacyclobutane incorporated in a pincer complex. The coordination of different coligands to the nickelacyclobutane determines its selective decomposition along cyclopropanation, metathesis or apparent b-hydride elimination pathways. DFT calculations shed light on the mechanism of these different pathways.Scheme 1. Metallacyclobutane decomposition.

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confidence: 99%

Divergent Reactivity of an Isolable Nickelacyclobutane

et al. 2021

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“…However, the calculated Ni–C a bond length (1.968 Å) is too long for any significant carbenic character, indeed it is longer than the Ni–C(NHC) bond (1.926 Å), which is generally accepted to be a single bond with very little retro-donation. By comparison, structurally characterized Ni(II) carbene complexes without heteroatom functionality on the carbene carbon display NiC bond lengths in the range 1.844–1.906 Å, while the Ni–C bond lengths of the very limited number of nickelacyclobutanes reported are 1.927–1.956 Å . Meanwhile, despite being marginally shorter than a typical C–C single bond, C b –C c is significantly longer than a double bond, even one coordinated to Ni, as highlighted by the calculated C–C bond length of 1.361 Å for the coordinated styrene ligand in I F .…”

Section: Mechanistic Studiesmentioning

confidence: 95%

Methylenespiro[2.3]hexanes via Nickel-Catalyzed Cyclopropanations with [1.1.1]Propellane

Noble

Bedford

et al. 2019

J. Am. Chem. Soc.

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Propellane is a highly strained tricyclic hydrocarbon whose reactivity is dominated by addition reactions across the central inverted bond to provide bicyclo[1.1.1]pentane derivatives. These reactions proceed under both radical and twoelectron pathways, hence providing access to a diverse array of products. Conversely, transition metal-catalyzed reactions of [1.1.1]propellane are underdeveloped and lack synthetic utility, with reported examples generally yielding mixtures of ring-opened structural isomers, dimers, and trimers, often with poor selectivity. Herein, we report that nickel(0) catalysis enables the use of [1.1.1]propellane as a carbene precursor in cyclopropanations of a range of functionalized alkenes to give methylenespiro[2.3]hexane products. Computational studies provide support for initial formation of a Ni(0)-[1.1.1]propellane complex followed by concerted double CC bond activation to give the key 3-methylenecyclobutylidene-nickel intermediate.

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“…Dimethylenecyclobutane. Very little is known about the organometallic chemistry of perfluoro-1,2-dimethylenecyclobutane (45), the dimer of tetrafluoroallene. We have reported a manganese complex 46 containing this bridged diene ligand, obtained photochemically from CpMn(CO) 3 and 45 (Scheme 13).…”

Section: Conjugated Dienesmentioning

confidence: 99%

“…Hughes, and complexes of both early and late transition-metals have been structurally characterised. [43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58] The great variability in coordination modes is unprecedented by any other fluorinated molecule. However, the scope of OFCOT chemistry exceeds this perspective article, therefore only a brief overview based on representative examples will be given; a comprehensive review has been published by Hughes.…”

Section: Conjugated Dienesmentioning

confidence: 99%

Fluorinated dienes in transition-metal chemistry – the rich chemistry of electron-poor ligands

Kuehnel

Lentz

2010

Dalton Trans.

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The coordination chemistry of alkenes is among the fundamentals of organometallic chemistry. However, despite the beneficial effects of fluorination to organic molecules, their fluorinated counterparts are rarely found in transition-metal complexes and most examples are limited to simple monoalkenes like tetrafluoroethene. The paucity of fluorodiene complexes is contrasted by their structural diversity. Seemingly similar dienes containing conjugated, isolated or cumulated double bonds exhibit largely different ligand properties. While the most prominent group, the conjugated fluorodienes, is very flexible in hapticity, their analogues bearing isolated double bonds behave more like monoalkenes. Fluorinated cumulenes in contrast are thermally labile, their chemistry is dominated by the stabilising effect of metal coordination. This review outlines the synthesis, structure and reactivity of transition-metal complexes derived from fluorinated dienes.

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Transition-metal chemistry of octafluorocyclooctatetraene. Synthesis and x-ray structure of a novel five-coordinate cis-dialkylnickel complex

Cited by 9 publications

References 1 publication

Divergent Reactivity of an Isolable Nickelacyclobutane

Divergent Reactivity of an Isolable Nickelacyclobutane

Methylenespiro[2.3]hexanes via Nickel-Catalyzed Cyclopropanations with [1.1.1]Propellane

Fluorinated dienes in transition-metal chemistry – the rich chemistry of electron-poor ligands

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