Snapshot of cyclooctyne ring-opening to a tethered alkylidene cyclic polymer catalyst

Javier M. Hurst; Rinku Yadav; Parker T. Boeck; Ion Ghiviriga; Christi Anna L. Brantley; Łukasz Dobrzycki; Adam S. Veige

doi:10.1039/d4sc04411h

Snapshot of cyclooctyne ring-opening to a tethered alkylidene cyclic polymer catalyst

Javier M. Hurst, Rinku Yadav, Parker T. Boeck, Ion Ghiviriga, Christi Anna L. Brantley, Łukasz Dobrzycki, Adam S. Veige

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

2 Scopus citations

Abstract

Cyclooctyne reacts with the trianionic pincer ligand supported alkylidyne [^tBuOCO]WCC(CH₃)₃(THF)₂ (1) to yield tungstacyclopropene (3) and tungstacyclopentadiene (4) complexes. The ratio of 3 and 4 in the reaction mixture depends on the stoichiometry of the reaction. The maximum concentration of 3 occurs with one equiv. of cyclooctyne and 4 is the exclusive product of the reaction above three equivalents. Both complexes 3 and 4 convert to the cyclooctyne ring-opened product 5 upon heating. While the conversion of 4 to 5 is accompanied by formation of polycyclooctyne as a white precipitate during the reaction, conversion of 3 to 5 is homogeneous. Exhibiting Ring Expansion Polymerization (REP), complexes 4 and 5 initiate the polymerization of phenylacetylene to generate cyclic poly(phenylacetylene) (c-PPA).

Original language	English
Pages (from-to)	15873-15879
Number of pages	7
Journal	Chemical Science
Volume	15
Issue number	38
DOIs	https://doi.org/10.1039/d4sc04411h
State	Published - Aug 30 2024
Externally published	Yes

Funding

This material is based upon work supported by the National Science Foundation CHE-2154377 (A. S. V.). The GC/EI-MS instrument is funded by NIH S10 OD021758-01A1. LD acknowledges the NSF (CHE-1828064) and UF for the purchase of X-ray equipment.

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title = "Snapshot of cyclooctyne ring-opening to a tethered alkylidene cyclic polymer catalyst",

abstract = "Cyclooctyne reacts with the trianionic pincer ligand supported alkylidyne [tBuOCO]WCC(CH3)3(THF)2 (1) to yield tungstacyclopropene (3) and tungstacyclopentadiene (4) complexes. The ratio of 3 and 4 in the reaction mixture depends on the stoichiometry of the reaction. The maximum concentration of 3 occurs with one equiv. of cyclooctyne and 4 is the exclusive product of the reaction above three equivalents. Both complexes 3 and 4 convert to the cyclooctyne ring-opened product 5 upon heating. While the conversion of 4 to 5 is accompanied by formation of polycyclooctyne as a white precipitate during the reaction, conversion of 3 to 5 is homogeneous. Exhibiting Ring Expansion Polymerization (REP), complexes 4 and 5 initiate the polymerization of phenylacetylene to generate cyclic poly(phenylacetylene) (c-PPA).",

author = "Hurst, {Javier M.} and Rinku Yadav and Boeck, {Parker T.} and Ion Ghiviriga and Brantley, {Christi Anna L.} and {\L}ukasz Dobrzycki and Veige, {Adam S.}",

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doi = "10.1039/d4sc04411h",

language = "English",

volume = "15",

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T1 - Snapshot of cyclooctyne ring-opening to a tethered alkylidene cyclic polymer catalyst

AU - Hurst, Javier M.

AU - Yadav, Rinku

AU - Boeck, Parker T.

AU - Ghiviriga, Ion

AU - Brantley, Christi Anna L.

AU - Dobrzycki, Łukasz

AU - Veige, Adam S.

PY - 2024/8/30

Y1 - 2024/8/30

N2 - Cyclooctyne reacts with the trianionic pincer ligand supported alkylidyne [tBuOCO]WCC(CH3)3(THF)2 (1) to yield tungstacyclopropene (3) and tungstacyclopentadiene (4) complexes. The ratio of 3 and 4 in the reaction mixture depends on the stoichiometry of the reaction. The maximum concentration of 3 occurs with one equiv. of cyclooctyne and 4 is the exclusive product of the reaction above three equivalents. Both complexes 3 and 4 convert to the cyclooctyne ring-opened product 5 upon heating. While the conversion of 4 to 5 is accompanied by formation of polycyclooctyne as a white precipitate during the reaction, conversion of 3 to 5 is homogeneous. Exhibiting Ring Expansion Polymerization (REP), complexes 4 and 5 initiate the polymerization of phenylacetylene to generate cyclic poly(phenylacetylene) (c-PPA).

AB - Cyclooctyne reacts with the trianionic pincer ligand supported alkylidyne [tBuOCO]WCC(CH3)3(THF)2 (1) to yield tungstacyclopropene (3) and tungstacyclopentadiene (4) complexes. The ratio of 3 and 4 in the reaction mixture depends on the stoichiometry of the reaction. The maximum concentration of 3 occurs with one equiv. of cyclooctyne and 4 is the exclusive product of the reaction above three equivalents. Both complexes 3 and 4 convert to the cyclooctyne ring-opened product 5 upon heating. While the conversion of 4 to 5 is accompanied by formation of polycyclooctyne as a white precipitate during the reaction, conversion of 3 to 5 is homogeneous. Exhibiting Ring Expansion Polymerization (REP), complexes 4 and 5 initiate the polymerization of phenylacetylene to generate cyclic poly(phenylacetylene) (c-PPA).

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U2 - 10.1039/d4sc04411h

DO - 10.1039/d4sc04411h

M3 - Article

AN - SCOPUS:85205039931

SN - 2041-6520

VL - 15

SP - 15873

EP - 15879

JO - Chemical Science

JF - Chemical Science

IS - 38

ER -

Snapshot of cyclooctyne ring-opening to a tethered alkylidene cyclic polymer catalyst

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