Copolymerization of cycloalkenes as a probe of the propagation steps in olefin metathesis

被引:13
作者
AmirEbrahimi, V [1 ]
Carvill, AG [1 ]
Hamilton, JG [1 ]
Rooney, JJ [1 ]
Tuffy, C [1 ]
机构
[1] QUEENS UNIV BELFAST,SCH CHEM,BELFAST BT9 5AG,ANTRIM,NORTH IRELAND
关键词
cycloalkene copolymerization; ruthenium; osmium;
D O I
10.1016/S1381-1169(96)00086-6
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A range of ring-opened metathesis copolymers of norbornene and cyclopentene have been prepared and C-13 NMR spectroscopy used to analyse in detail the nature of the homo and heterodyad units. This has provided significant new information on the sensitivity of the [2 + 2] cycloaddition step in metathesis to the steric and electronic factors associated with the [Mt]=C and C=C moieties involved. Novel very high cis directing catalyst systems, have also been developed for the homopolymerization of norbornene using various ethers with Mo and W-based catalyst systems or chelating dienes and phenylacetylene with RuCl3 and OsCl3 systems. The general feature of cis/trans blockiness at high cis content is investigated in much greater detail. A clearer description of the associated relaxation processes of the propagating species emerges from this work. The metathesis polymerization of the matched pair, benzonorbornadiene and 7-oxa-benzonorbornadiene has been investigated using Ru and Os-based initiators. The results illustrate the subtle way whereby the presence of the proximate 7-O-atom may facilitate [2 + 2] cycloadditions. This constitutes a valuable novel method of studying key electronic factors in the mechanism of the metathesis reaction.
引用
收藏
页码:85 / 94
页数:10
相关论文
共 18 条
  • [1] AMIREBRAHIMI V, UNPUYB
  • [2] AMIREBRAHIMI V, UNPUB
  • [3] MICROSTRUCTURE OF RING-OPENED POLYMERS AND COPOLYMERS OF NORBORNADIENE
    BELL, B
    HAMILTON, JG
    MACKEY, OND
    ROONEY, JJ
    [J]. JOURNAL OF MOLECULAR CATALYSIS, 1992, 77 (01): : 61 - 73
  • [4] CARBON-HYDROGEN-TRANSITION METAL BONDS
    BROOKHART, M
    GREEN, MLH
    [J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1983, 250 (01) : 395 - 408
  • [5] A CYCLOMETALATED ARYLOXY(CHLORO)NEOPENTYLIDENETUNGSTEN COMPLEX - A HIGHLY-ACTIVE AND STEREOSELECTIVE CATALYST FOR THE METATHESIS OF CIS-2-PENTENE, AND TRANS-2-PENTENE, NORBORNENE, 1-METHYL-NORBORNENE, AND ETHYL OLEATE
    COUTURIER, JL
    PAILLET, C
    LECONTE, M
    BASSET, JM
    WEISS, K
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1992, 31 (05): : 628 - 631
  • [6] ENESCU L, 1989, REV ROUM CHIM, V32, P765
  • [7] FAWCETT AH, 1996, POLYM SPECTROSCOPY
  • [8] THE MECHANISM OF STEREOSELECTIVE RING-OPENING METATHESIS POLYMERIZATION OF NORBORNENE AND SEVERAL DERIVATIVES
    GILLAN, EMD
    HAMILTON, JG
    MACKEY, OND
    ROONEY, JJ
    [J]. JOURNAL OF MOLECULAR CATALYSIS, 1988, 46 (1-3): : 359 - 371
  • [9] RING-OPENING POLYMERIZATION OF ENDO AND EXO-DICYCLOPENTADIENE AND THEIR 7,8-DIHYDRO DERIVATIVES
    HAMILTON, JG
    IVIN, KJ
    ROONEY, JJ
    [J]. JOURNAL OF MOLECULAR CATALYSIS, 1986, 36 (1-2): : 115 - 125
  • [10] HAMILTON JG, 1993, MAKROMOL CHEM, V194, P2907