TY - JOUR
T1 - Transition metal carbonyl catalysts for polymerizations of substituted acetylenes
AU - Xu, Kaitian
AU - Peng, Han
AU - Lam, Jacky Wing Yip
AU - Poon, Tommy Wan Hong
AU - Dong, Yuping
AU - Xu, Hongyao
AU - Sun, Qunhui
AU - Cheuk, Kevin Ka Leung
AU - Salhi, Fouad
AU - Lee, Priscilla Pui Sze
AU - Tang, Ben Zhong
PY - 2000/9/19
Y1 - 2000/9/19
N2 - Most of the existing metal carbonyl catalysts for acetylene polymerizations need to be preactivated by chlorine-containing additives or by UV irradiation in halogenated solvents. In this work, we developed a series of `simple' metal carbonyl catalysts of general structure M(CO)xLy (M = Mo, W), none of which require additives or pre-photoirradiation, most of which are air- and moisture-stable, and some of which work well in nonhalogenated solvents. The acetonitrile complexes M(CO)3(NCCH3)3 initiated polymerizations of a variety of mono- and disubstituted acetylenes at room temperature. The arene and diene complexes W(CO)3(mes) and Mo(CO)3(nbd) (mes = mesitylene, nbd = 2,5-norbornadiene) are tolerant of polar groups and effected polymerizations of functional acetylenes containing ester, ether, and cyano groups. The halogenated complexes MI2(CO)3(NCCH3)2 catalyzed polymerizations of phenylacetylene in toluene. The chlorine-containing acetylene monomers ClC triple bond CC6H5 and ClC triple bond CC6H13 were readily polymerized by the Mo complexes in nonhalogenated solvents such as toluene and dioxane, giving polymers with high molecular weights (Mw up to 883×103) in high yields (up to 100%).
AB - Most of the existing metal carbonyl catalysts for acetylene polymerizations need to be preactivated by chlorine-containing additives or by UV irradiation in halogenated solvents. In this work, we developed a series of `simple' metal carbonyl catalysts of general structure M(CO)xLy (M = Mo, W), none of which require additives or pre-photoirradiation, most of which are air- and moisture-stable, and some of which work well in nonhalogenated solvents. The acetonitrile complexes M(CO)3(NCCH3)3 initiated polymerizations of a variety of mono- and disubstituted acetylenes at room temperature. The arene and diene complexes W(CO)3(mes) and Mo(CO)3(nbd) (mes = mesitylene, nbd = 2,5-norbornadiene) are tolerant of polar groups and effected polymerizations of functional acetylenes containing ester, ether, and cyano groups. The halogenated complexes MI2(CO)3(NCCH3)2 catalyzed polymerizations of phenylacetylene in toluene. The chlorine-containing acetylene monomers ClC triple bond CC6H5 and ClC triple bond CC6H13 were readily polymerized by the Mo complexes in nonhalogenated solvents such as toluene and dioxane, giving polymers with high molecular weights (Mw up to 883×103) in high yields (up to 100%).
UR - http://www.scopus.com/inward/record.url?scp=17444433924&partnerID=8YFLogxK
U2 - 10.1021/ma000843a
DO - 10.1021/ma000843a
M3 - Article
AN - SCOPUS:17444433924
SN - 0024-9297
VL - 33
SP - 6918
EP - 6924
JO - Macromolecules
JF - Macromolecules
IS - 19
ER -