Hurst Javier M, Yadav Rinku, Boeck Parker T, Ghiviriga Ion, Brantley ChristiAnna L, Dobrzycki Łukasz, Veige Adam S
University of Florida, Department of Chemistry, Center for Catalysis P.O. Box 117200 Gainesville FL 32611 USA
University of Florida, Department of Chemistry, George and Josephine Butler Polymer Research Laboratory, Center for Macromolecular Sciences and Engineering Gainesville FL 32611 USA.
Chem Sci. 2024 Aug 30;15(38):15873-9. doi: 10.1039/d4sc04411h.
Cyclooctyne reacts with the trianionic pincer ligand supported alkylidyne [ BuOCO]WCC(CH)(THF) (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).
环辛炔与三阴离子钳形配体支持的亚烷基[BuOCO]W≡C(CH)(THF)（1）反应，生成钨杂环丙烯（3）和钨杂环戊二烯（4）配合物。反应混合物中3和4的比例取决于反应的化学计量比。3的最大浓度出现在环辛炔为1当量时，而4是超过3当量反应的唯一产物。加热时，配合物3和4都会转化为环辛炔开环产物5。虽然4转化为5的过程中伴随着多环辛炔作为白色沉淀的生成，但3转化为5是均相的。配合物4和5表现出扩环聚合（REP），引发苯乙炔聚合生成环状聚（苯乙炔）（c-PPA）。
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