We report the synthesis of O- and N-chelated hexacoordinated molybdenum imido alkylidene N-heterocyclic carbene (NHC) bistriflate and pentacoordinated molybdenum imido alkylidene NHC monotriflate monoalkoxide complexes and their use as thermally latent and in some cases air-stable precatalysts in the ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD). Introduction of electron-withdrawing and electron-donating groups at the O-chelated alkylidene ligand allowed for the tuning of both the onset temperature of polymerization (Tonset) and the temperature of the exotherm maximum (Texo,max). In addition, N-chelated complexes were synthesized using easily available 2-vinylpyridine or 2-vinyl-N,N-dimethylaniline to yield five-membered and, for the first time, four-membered molybdenum imido alkylidene NHC chelates. With these precatalysts, Tonset and Texo,max could be varied between 52 and 142 °C and between 99 and 174 °C, respectively.
Description
Tuning the Latent Behavior of Molybdenum Imido Alkylidene N‑Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization
%0 Journal Article
%1 doi:10.1021/acs.organomet.0c00740
%A Momin, Mohasin
%A Musso, Janis V.
%A Frey, Wolfgang
%A Buchmeiser, Michael R.
%D 0
%J Organometallics
%K crc1333 crc1333_fp1
%N 0
%P null
%R 10.1021/acs.organomet.0c00740
%T Tuning the Latent Behavior of Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization
%U https://doi.org/10.1021/acs.organomet.0c00740
%V 0
%X We report the synthesis of O- and N-chelated hexacoordinated molybdenum imido alkylidene N-heterocyclic carbene (NHC) bistriflate and pentacoordinated molybdenum imido alkylidene NHC monotriflate monoalkoxide complexes and their use as thermally latent and in some cases air-stable precatalysts in the ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD). Introduction of electron-withdrawing and electron-donating groups at the O-chelated alkylidene ligand allowed for the tuning of both the onset temperature of polymerization (Tonset) and the temperature of the exotherm maximum (Texo,max). In addition, N-chelated complexes were synthesized using easily available 2-vinylpyridine or 2-vinyl-N,N-dimethylaniline to yield five-membered and, for the first time, four-membered molybdenum imido alkylidene NHC chelates. With these precatalysts, Tonset and Texo,max could be varied between 52 and 142 °C and between 99 and 174 °C, respectively.
@article{doi:10.1021/acs.organomet.0c00740,
abstract = { We report the synthesis of O- and N-chelated hexacoordinated molybdenum imido alkylidene N-heterocyclic carbene (NHC) bistriflate and pentacoordinated molybdenum imido alkylidene NHC monotriflate monoalkoxide complexes and their use as thermally latent and in some cases air-stable precatalysts in the ring-opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD). Introduction of electron-withdrawing and electron-donating groups at the O-chelated alkylidene ligand allowed for the tuning of both the onset temperature of polymerization (Tonset) and the temperature of the exotherm maximum (Texo,max). In addition, N-chelated complexes were synthesized using easily available 2-vinylpyridine or 2-vinyl-N,N-dimethylaniline to yield five-membered and, for the first time, four-membered molybdenum imido alkylidene NHC chelates. With these precatalysts, Tonset and Texo,max could be varied between 52 and 142 °C and between 99 and 174 °C, respectively. },
added-at = {2021-01-19T13:18:00.000+0100},
author = {Momin, Mohasin and Musso, Janis V. and Frey, Wolfgang and Buchmeiser, Michael R.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2e831a961be2a48acdfebc9edb223c157/dr.ruethlein},
description = {Tuning the Latent Behavior of Molybdenum Imido Alkylidene N‑Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization},
doi = {10.1021/acs.organomet.0c00740},
eprint = {https://doi.org/10.1021/acs.organomet.0c00740},
interhash = {e6d1bfc9976658cd8748cf4d61913d31},
intrahash = {e831a961be2a48acdfebc9edb223c157},
journal = {Organometallics},
keywords = {crc1333 crc1333_fp1},
number = 0,
pages = {null},
timestamp = {2021-01-26T10:09:36.000+0100},
title = {Tuning the Latent Behavior of Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes in Dicyclopentadiene Polymerization},
url = {https://doi.org/10.1021/acs.organomet.0c00740},
volume = 0,
year = 0
}
