Probing tungsten-alkylidyne cyclic polymer initiator decomposition pathways with oxidants

Rinku Yadav; Christi Anna L. Brantley; Ion Ghiviriga; Khalil A. Abboud; Daniel W. Lester; Adam S. Veige

doi:10.1016/j.poly.2024.116987

Probing tungsten-alkylidyne cyclic polymer initiator decomposition pathways with oxidants

Rinku Yadav, Christi Anna L. Brantley, Ion Ghiviriga, Khalil A. Abboud, Daniel W. Lester, Adam S. Veige

Research output: Contribution to journal › Article › peer-review

Abstract

An OCO-pincer supported tungsten(VI) alkylidyne exhibits diverse reactivity depending on the identity of the oxidizing agent and the stoichiometry of the reaction. Oxidation reactions are studied with azo, nitroso, and oxo compounds. Benzo(c)cinnoline facilitates migratory insertion of the alkylidyne carbon in the pincer backbone forming a tethered tungsten (VI) alkylidene complex. Analogous azobenzene activates a C[sbnd]C bond in the tert—butyl group of the alkylidyne and results in a tungsten di-imido complex. Nitrosobenzene and pyridine N-oxide undergo oxygen atom transfer (OAT) reactions and result in tungsten oxo complexes. Reactions with nitrosobenzene are sensitive to stoichiometry; C[sbnd]C bond activation is observed in stoichiometric reactions, while only OAT occurs with excess nitrosobenzene.

Original language	English
Article number	116987
Journal	Polyhedron
Volume	256
DOIs	https://doi.org/10.1016/j.poly.2024.116987
State	Published - Jul 1 2024
Externally published	Yes

Keywords

Alkylidene
Alkylidyne
Cyclic polymer
C–C bond activation
Oxygen atom transfer

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10.1016/j.poly.2024.116987

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title = "Probing tungsten-alkylidyne cyclic polymer initiator decomposition pathways with oxidants",

abstract = "An OCO-pincer supported tungsten(VI) alkylidyne exhibits diverse reactivity depending on the identity of the oxidizing agent and the stoichiometry of the reaction. Oxidation reactions are studied with azo, nitroso, and oxo compounds. Benzo(c)cinnoline facilitates migratory insertion of the alkylidyne carbon in the pincer backbone forming a tethered tungsten (VI) alkylidene complex. Analogous azobenzene activates a C[sbnd]C bond in the tert—butyl group of the alkylidyne and results in a tungsten di-imido complex. Nitrosobenzene and pyridine N-oxide undergo oxygen atom transfer (OAT) reactions and result in tungsten oxo complexes. Reactions with nitrosobenzene are sensitive to stoichiometry; C[sbnd]C bond activation is observed in stoichiometric reactions, while only OAT occurs with excess nitrosobenzene.",

keywords = "Alkylidene, Alkylidyne, Cyclic polymer, C–C bond activation, Oxygen atom transfer",

author = "Rinku Yadav and Brantley, {Christi Anna L.} and Ion Ghiviriga and Abboud, {Khalil A.} and Lester, {Daniel W.} and Veige, {Adam S.}",

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doi = "10.1016/j.poly.2024.116987",

language = "English",

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T1 - Probing tungsten-alkylidyne cyclic polymer initiator decomposition pathways with oxidants

AU - Yadav, Rinku

AU - Brantley, Christi Anna L.

AU - Ghiviriga, Ion

AU - Abboud, Khalil A.

AU - Lester, Daniel W.

AU - Veige, Adam S.

PY - 2024/7/1

Y1 - 2024/7/1

N2 - An OCO-pincer supported tungsten(VI) alkylidyne exhibits diverse reactivity depending on the identity of the oxidizing agent and the stoichiometry of the reaction. Oxidation reactions are studied with azo, nitroso, and oxo compounds. Benzo(c)cinnoline facilitates migratory insertion of the alkylidyne carbon in the pincer backbone forming a tethered tungsten (VI) alkylidene complex. Analogous azobenzene activates a C[sbnd]C bond in the tert—butyl group of the alkylidyne and results in a tungsten di-imido complex. Nitrosobenzene and pyridine N-oxide undergo oxygen atom transfer (OAT) reactions and result in tungsten oxo complexes. Reactions with nitrosobenzene are sensitive to stoichiometry; C[sbnd]C bond activation is observed in stoichiometric reactions, while only OAT occurs with excess nitrosobenzene.

AB - An OCO-pincer supported tungsten(VI) alkylidyne exhibits diverse reactivity depending on the identity of the oxidizing agent and the stoichiometry of the reaction. Oxidation reactions are studied with azo, nitroso, and oxo compounds. Benzo(c)cinnoline facilitates migratory insertion of the alkylidyne carbon in the pincer backbone forming a tethered tungsten (VI) alkylidene complex. Analogous azobenzene activates a C[sbnd]C bond in the tert—butyl group of the alkylidyne and results in a tungsten di-imido complex. Nitrosobenzene and pyridine N-oxide undergo oxygen atom transfer (OAT) reactions and result in tungsten oxo complexes. Reactions with nitrosobenzene are sensitive to stoichiometry; C[sbnd]C bond activation is observed in stoichiometric reactions, while only OAT occurs with excess nitrosobenzene.

KW - Alkylidene

KW - Alkylidyne

KW - Cyclic polymer

KW - C–C bond activation

KW - Oxygen atom transfer

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U2 - 10.1016/j.poly.2024.116987

DO - 10.1016/j.poly.2024.116987

M3 - Article

AN - SCOPUS:85190343778

SN - 0277-5387

VL - 256

JO - Polyhedron

JF - Polyhedron

M1 - 116987

ER -

Probing tungsten-alkylidyne cyclic polymer initiator decomposition pathways with oxidants

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Keywords

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