Synthesis of Allenylidene Lithium and Silver Complexes, and Subsequent Transmetalation Reactions

Asay, Matthew; Donnadieu, Bruno; Schoeller, Wolfgang&emsp;W.; Bertrand, Guy

doi:10.1002/ange.200901319

Cited by 10 publications

(8 citation statements)

References 71 publications

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“…523 The group of Bertrand has published a series of NHCderived allenylidene coinage metal complexes (e.g., 475−477, Figure 55). 437,524 Their syntheses are based on the reactivity of respective acetylenyl-substituted NHCs.…”

Section: Chemical Reviewsmentioning

confidence: 99%

NHCs in Main Group Chemistry

et al. 2018

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Since the discovery of the first stable N-heterocyclic carbene (NHC) in the beginning of the 1990s, these divalent carbon species have become a common and available class of compounds, which have found numerous applications in academic and industrial research. Their important role as two-electron donor ligands, especially in transition metal chemistry and catalysis, is difficult to overestimate. In the past decade, there has been tremendous research attention given to the chemistry of low-coordinate main group element compounds. Significant progress has been achieved in stabilization and isolation of such species as Lewis acid/base adducts with highly tunable NHC ligands. This has allowed investigation of numerous novel types of compounds with unique electronic structures and opened new opportunities in the rational design of novel organic catalysts and materials. This Review gives a general overview of this research, basic synthetic approaches, key features of NHC-main group element adducts, and might be useful for the broad research community.

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Section: Chemical Reviewsmentioning

confidence: 99%

NHCs in Main Group Chemistry

et al. 2018

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“…Scheme 2). [5,6] The main object of the present study was to explain these data. [5,6] The main object of the present study was to explain these data.…”

Section: Introductionmentioning

confidence: 99%

Stable Carbenes or Betaines?

Kleinpeter

Koch

2018

Eur J Org Chem

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The anisotropy effect in 1H NMR spectroscopy can be readily employed to indicate the position of carbene/betaine mesomeric equilibria. NR2 substituted carbene/betaines tend to adopt betaine structures, whereas in the absence of NR2 substituents, the betaine structures cannot stabilise the structure through both π‐donation effects of the NMe2 groups and the electronegativity of the nitrogen atoms, and the corresponding carbene‐like structures are preferred. These conclusions are supported by calculated bond orders and δ(13C)/ppm values. The spatial magnetic properties of isonitriles and carbon monoxide, which can be counted as stable carbenes or, at least, as carbene‐analogues, also exist as stable betaine structures, which is again supported by structural and magnetic properties.

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“…In addition to the carbocation from carbocation sources (see Scheme 5: 8,9 / 10,11), the neutral Lewis acid BF 3 likewise added to the nitrogen atom of 8 to give an neutral allenylidene-type complex. Compound 12 (Scheme 6), isolated in 54% yield, turned out to be rather labile and quickly decomposed on contact with air.…”

Section: Preparative and Spectroscopic Resultsmentioning

confidence: 99%

“…Although allenylidene complexes of several transition metals are now known for quite some time, the synthesis of the first stable palladium allenylidene complexes has been reported only recently [10,11]. Analogously, until now only one nickel allenylidene complex has been described by Butenschön et al [12].…”

Section: Introductionmentioning

confidence: 96%