Probing tungsten-alkylidyne cyclic polymer initiator decomposition pathways with oxidants

被引：0

作者：

Yadav, Rinku ^{[1
]}

Brantley, ChristiAnna L. ^{[1
]}

Ghiviriga, Ion ^{[2
]}

Abboud, Khalil A. ^{[1
]}

Lester, Daniel W. ^{[3
]}

Veige, Adam S. ^{[1
]}

机构：

[1] Univ Florida, Dept Chem, Ctr Catalysis, POB 117200, Gainesville, FL 32611 USA

[2] Univ Florida, Ctr NMR Spect, Dept Chem, POB 117200, Gainesville, FL 32611 USA

[3] Univ Warwick, Polymer Characterizat Res Technol Platform, Coventry CV4 7AL, England

来源：

POLYHEDRON | 2024年 / 256卷

基金：

美国国家科学基金会;

关键词：

Alkylidyne; Alkylidene; C-C bond activation; Cyclic polymer; Oxygen atom transfer; OPENING METATHESIS POLYMERIZATION; OLEFIN METATHESIS; NITROSO-COMPOUNDS; LINEAR POLY(DIMETHYLSILOXANES); 4-ELECTRON REDUCTION; TRIANIONIC PINCER; METALLACYCLOBUTANE DEPROTONATION; HYDRODYNAMIC PROPERTIES; CATALYST DECOMPOSITION; GRUBBS CATALYSTS;

D O I：

10.1016/j.poly.2024.116987

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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-C bond in the tert-butyl group of the alkylidyne and results in a tungsten di-imido complex. Nitrosobenzene and pyridine Noxide undergo oxygen atom transfer (OAT) reactions and result in tungsten oxo complexes. Reactions with nitrosobenzene are sensitive to stoichiometry; C-C bond activation is observed in stoichiometric reactions, while only OAT occurs with excess nitrosobenzene.

引用

页数：12