RING-OPENING METHATHESIS POLYMERIZATION OF (+)(-) AND (+/-)-ENDO,EXO-5,6-DIMETHYLBICYCLO[2.2.1]HEPT-2-ENE BY MO(CH-T-BU)(N-2,6-C6H3-I-PR2)(OR)2

被引:27
作者
SUNAGA, T [1 ]
IVIN, KJ [1 ]
HOFMEISTER, GE [1 ]
OSKAM, JH [1 ]
SCHROCK, RR [1 ]
机构
[1] MIT,DEPT CHEM,6-331,CAMBRIDGE,MA 02139
关键词
D O I
10.1021/ma00093a003
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Ring-opened polymers of (+)- and (+/-)-endo,exo-5,6-dimethylbicyclo[2.2.1]hept-2-ene(1) having cis double bond contents between 5 and 85% were prepared using Mo(CH-t-Bu)(NAr)(OR)2 (Ar = 2,6-C6H3-i-Pr2; OR = OCMe3, OCMe2(CF3), OCMe(CFS)2) complexes as initiators. The cis content of the polymers increased in proportion to the electron-withdrawing power of the alkoxide ligands. C-13 NMR spectra (125 MHz) of these polymers were interpreted in terms of the various possible diad structures. XX, XN (NX), and NN, where X and N refer to substituents derived from exo and endo methyl groups, m and r refer to the meso (isotactic) or racemic (syndiotactic) configuration of adjacent cyclopentane rings in the chain, and tt, tc (ct), and cc refer to the cis/trans double bond sequences. High-cis polymer made from 98% (+)-1 contained 78% m diads and had more than twice the optical rotatory power and a higher T, (85-degrees-C) than the high-trans polymer (48% m diads; T, = 55-degrees-C).
引用
收藏
页码:4043 / 4050
页数:8
相关论文
共 26 条
[1]   POLYMERIZATION OF FUNCTIONALIZED NORBORNENES EMPLOYING MO(CH-T-BU)(NAR)(O-T-BU)2 AS THE INITIATOR [J].
BAZAN, GC ;
SCHROCK, RR ;
CHO, HN ;
GIBSON, VC .
MACROMOLECULES, 1991, 24 (16) :4495-4502
[2]   LIVING RING-OPENING METATHESIS POLYMERIZATION OF 2,3-DIFUNCTIONALIZED NORBORNADIENES BY MO(CH-TERT-BU)(N-2,6-C6H3-ISO-PR2)(O-TERT-BU)2 [J].
BAZAN, GC ;
KHOSRAVI, E ;
SCHROCK, RR ;
FEAST, WJ ;
GIBSON, VC ;
OREGAN, MB ;
THOMAS, JK ;
DAVIS, WM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (23) :8378-8387
[3]   LIVING RING-OPENING METATHESIS POLYMERIZATION OF 2,3-DIFUNCTIONALIZED 7-OXANORBORNENES AND 7-OXANORBORNADIENES BY MO(CHCME2R)(N-2,6-C6H3-ISO-PR2)(O-TERT-BU)2 AND MO(CHCME2R)(N-2,6-C6H3-ISO-PR2)(OCME2CF3)2 [J].
BAZAN, GC ;
OSKAM, JH ;
CHO, HN ;
PARK, LY ;
SCHROCK, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (18) :6899-6907
[4]  
FEAST WJ, 1992, MAKROMOL CHEM, V193, P2103
[5]   A REMARKABLE ANCILLARY LIGAND EFFECT IN LIVING RING-OPENING METATHESIS POLYMERIZATION [J].
FEAST, WJ ;
GIBSON, VC ;
MARSHALL, EL .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1992, (16) :1157-1158
[6]  
FEAST WJ, IN PRESS J MOL CATAL
[7]   SIMPLE, HIGH-YIELD SYNTHESES OF MOLYBDENUM(VI) BIS(IMIDO) COMPLEXES OF THE TYPE MO(NR)2CL2(1,2-DIMETHOXYETHANE) [J].
FOX, HH ;
YAP, KB ;
ROBBINS, J ;
CAI, S ;
SCHROCK, RR .
INORGANIC CHEMISTRY, 1992, 31 (11) :2287-2289
[8]   ASYMMETRIC DIELS-ALDER REACTION - COOPERATIVE BLOCKING EFFECT IN ORGANIC-SYNTHESIS [J].
FURUTA, K ;
IWANAGA, K ;
YAMAMOTO, H .
TETRAHEDRON LETTERS, 1986, 27 (37) :4507-4510
[9]  
GREENE RME, 1986, MAKROMOL CHEM, V187, P619
[10]  
GREENE RME, 1987, MAKROMOL CHEM, V188, P1933