2020
DOI: 10.1039/d0cc04426a
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A metastable RuIII azido complex with metallo-Staudinger reactivity

Abstract: The metastable purple [(Py5Me2)RuIII(N3)]2+ species undergoes a reaction with PPh3 at room temperature to form the RuII phosphinimine complex [(Py5Me2)RuII(N(H)PPh3)]2+ and free [H2NPPh3]+ observed in a combined 23% conversion. Mechanistic...

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Cited by 3 publications
(6 citation statements)
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“…However, no intermediates were observed by NMR spectroscopy, and more detailed kinetic analyses were hampered by side products. Mechanisms involving the direct reaction of the bridging azide with both PMe 3 and aliphatic C–H bonds are also possible. We thus turned to the following computational study in order to validate the feasibility of a nitride intermediate and to identify the factors that govern the reaction pathways that emerge therefrom (see the Supporting Information for computations on azide-mediated pathways).…”
Section: Resultsmentioning
confidence: 99%
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“…However, no intermediates were observed by NMR spectroscopy, and more detailed kinetic analyses were hampered by side products. Mechanisms involving the direct reaction of the bridging azide with both PMe 3 and aliphatic C–H bonds are also possible. We thus turned to the following computational study in order to validate the feasibility of a nitride intermediate and to identify the factors that govern the reaction pathways that emerge therefrom (see the Supporting Information for computations on azide-mediated pathways).…”
Section: Resultsmentioning
confidence: 99%
“…Additionally, the presence of one obtuse N–P–C angle of 165°, along with a lengthening of the corresponding P–C distance, is consistent with back-donation to the P–C σ* orbital. A recent communication by Berry and co-workers also described the direct formation of a PN-containing product formed through the addition of phosphine to a coordinated azide . As discussed above, however, the range of PCET and C–H insertion chemistry performed by this system lends support to a nitride intermediate.…”
Section: Resultsmentioning
confidence: 99%
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“…Phosphinimines are an underutilized class of ligands for latetransition metals that are beginning to receive more and more attention, especially as chelating donors for catalytic applications. 42 Monodentate phosphinimines, however, are quite rare on ruthenium, 43 whereas monodentate phosphinimide complexes are a bit more common. 44−53 Moreover, while phosphinimides have been utilized in early transition-metalbased alkyne metathesis, 54 to the best of our knowledge, phosphinimines and phosphinimides have not been used in ruthenium-based OM catalysts.…”
Section: ■ Introductionmentioning
confidence: 99%
“…Phosphinimines are an underutilized class of ligands for late-transition metals that are beginning to receive more and more attention, especially as chelating donors for catalytic applications . Monodentate phosphinimines, however, are quite rare on ruthenium, whereas monodentate phosphinimide complexes are a bit more common. Moreover, while phosphinimides have been utilized in early transition-metal-based alkyne metathesis, to the best of our knowledge, phosphinimines and phosphinimides have not been used in ruthenium-based OM catalysts. What makes these ligands so intriguing is their unique electronic structure; they can act as both strong σ- and π-donors due to their ylide-like structure. , Therefore, it was thought that phosphinimines and/or phosphinimides would be well suited for stabilizing high oxidation state, coordinatively unsaturated ruthenium carbene complexes that are common intermediates during OM.…”
Section: Introductionmentioning
confidence: 99%