2023
DOI: 10.1002/anie.202218047
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Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion

Abstract: The cyaphide anion, CP−, is shown to undergo three distinct oligomerization reactions in the coordination sphere of metals. Reductive coupling of Au(IDipp)(CP) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) by Sm(Cp*)2(OEt2) (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl), was found to afford a tetra‐metallic complex containing a 2,3‐diphosphabutadiene‐1,1,4,4‐tetraide fragment. By contrast, non‐reductive dimerization of Ni(SIDipp)(Cp)(CP) (SIDipp=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolidin‐2‐ylidene; Cp… Show more

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Cited by 8 publications
(5 citation statements)
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“…We have recently developed a cyaphide‐transfer reagent with Grignard‐like reactivity that allows access to a variety of cyaphido metal complexes [29–31] . We have also gone on to show that inorganic click reactivity is common to a wide range of metal complexes containing a cyaphide ligand [32] .…”
Section: Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…We have recently developed a cyaphide‐transfer reagent with Grignard‐like reactivity that allows access to a variety of cyaphido metal complexes [29–31] . We have also gone on to show that inorganic click reactivity is common to a wide range of metal complexes containing a cyaphide ligand [32] .…”
Section: Methodsmentioning
confidence: 99%
“…We have recently developed a cyaphide-transfer reagent with Grignard-like reactivity that allows access to a variety of cyaphido metal complexes. [29][30][31] We have also gone on to show that inorganic click reactivity is common to a wide range of metal complexes containing a cyaphide ligand. [32] These cycloaddition reactions proceed rapidly, and in non-polar solvents, to selectively afford the metallo-triazaphospholes in high yields.…”
mentioning
confidence: 99%
“…We have recently developed a cyaphide‐transfer reagent with Grignard‐like reactivity that allows access to a variety of cyaphido metal complexes [29–31] . We have also gone on to show that inorganic click reactivity is common to a wide range of metal complexes containing a cyaphide ligand [32] .…”
Section: Methodsmentioning
confidence: 99%
“…Recently, our group has developed a magnesium cyaphide complex that acts as a cyaphide transfer reagent, offering a general route to a variety of metal cyaphido complexes by simple salt metathesis reactions. [19] We reasoned that the highly reactive nature of these metal cyaphide complexes, which are prone to oligomerization in formal [2 + 2] and [2 + 2 + 2] cycloaddition reactions, [20] should allow for facile 1,3-dipolar cycloadditions with organic azides. We have found that these reactions proceed straightforwardly for a broad range of cyaphide complexes under mild conditions in a manner reminiscent of classic "click" reactions.…”
Section: Introductionmentioning
confidence: 99%
“…We reasoned that the highly reactive nature of these metal cyaphide complexes, which are prone to oligomerization in formal [2+2] and [2+2+2] cycloaddition reactions, [20] should allow for facile 1,3‐dipolar cycloadditions with organic azides. We have found that these reactions proceed straightforwardly for a broad range of cyaphide complexes under mild conditions in a manner reminiscent of classic “click” reactions.…”
Section: Introductionmentioning
confidence: 99%