REACTIVITY OF (C5ME5)2SM WITH ARYL-SUBSTITUTED ALKENES - SYNTHESIS AND STRUCTURE OF A BIMETALLIC STYRENE COMPLEX THAT CONTAINS AN ETA-2-ARENE LANTHANIDE INTERACTION

被引:149
作者
EVANS, WJ
ULIBARRI, TA
ZILLER, JW
机构
[1] the Department of Chemistry, University of California, Irvine, Irvine
关键词
D O I
10.1021/ja00157a035
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
(C5Me5)2Sm (1) and (C5Me5)2Sm(THF)2 (2) isomerize cis-stilbene to trans-stilbene. The stoichiometric reaction of 1 with stilbene forms [(C5Me5)2Sm]2(μ-η2:η4-PhCHCHPh) (3). 1 reacts with styrene to form [(C5Me5)2Sm]2(μ- η2:η4-CH2CHPh) (4). In both 3 and 4, the two (C5Me5)2Sm units coordinate on opposite sides of the alkene bond such that the Sm–Sm vector bisects the bond at right angles. In each complex, phenyl carbon atoms are oriented to interact with one of the samarium centers. In 4, the Sm–C(C5Me5) distances range from 2.678 (18) to 2.847 (18) Å, the Sm–C(alkene) distances range from 2.537 (15) to 2.732 (15) Å, and two carbon atoms of the phenyl ring are positioned 2.772 (17) and 2.850 (16) Å from one samarium atom. 3 crystallizes from hexane in space group with a = 12.156 (6) A, b = 14.405 (9) Å, c = 15.628 (2) Å, and V = 2737 (2) Å3 with Z = 2 for Dcalcd = 1.24 g cm–3. 4 crystallizes from hexane in space group Pbca with a = 21.169 (4) Å, b = 17.663 (3) Å, c = 23.713 (5) Å, and V = 8866 (3) Å3 with Z = 8 for Dcalcd = 1.417 g cm–3. Least-squares refinement of the model based on 3134 observed reflections converged to a final RF = 6.2%. © 1990, American Chemical Society. All rights reserved.
引用
收藏
页码:219 / 223
页数:5
相关论文
共 50 条
[12]   SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF [(C5ME5)2SM]2C4PH2, A SAMARIUM ETA-2-COMPLEX DERIVED FROM AN ALKYNE [J].
EVANS, WJ ;
KEYER, RA ;
ZHANG, H ;
ATWOOD, JL .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1987, (11) :837-838
[13]  
EVANS WJ, 1981, INORG CHEM, V20, P4320, DOI 10.1021/ic50226a058
[14]   CATALYTIC ACTIVATION OF MOLECULAR-HYDROGEN IN ALKYNE HYDROGENATION REACTIONS BY LANTHANIDE METAL VAPOR REACTION-PRODUCTS [J].
EVANS, WJ ;
BLOOM, I ;
ENGERER, SC .
JOURNAL OF CATALYSIS, 1983, 84 (02) :468-476
[15]   REACTIVITY OF TRIMETHYLALUMINUM WITH (C5ME5)2SM(THF)2 - SYNTHESIS, STRUCTURE, AND REACTIVITY OF THE SAMARIUM METHYL COMPLEXES (C5ME5)2SM[MU-ME)ALME2(MU-ME)]2SM(C5ME5)2 AND (C5ME5)2SMME(THF) [J].
EVANS, WJ ;
CHAMBERLAIN, LR ;
ULIBARRI, TA ;
ZILLER, JW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (19) :6423-6432
[16]   SOLUTION SYNTHESIS AND CRYSTALLOGRAPHIC CHARACTERIZATION OF THE DIVALENT ORGANOSAMARIUM COMPLEXES (C5ME5)2SM(THF)2 AND [(C5ME5)SM(MU-I)(THF)2]2 [J].
EVANS, WJ ;
GRATE, JW ;
CHOI, HW ;
BLOOM, I ;
HUNTER, WE ;
ATWOOD, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (04) :941-946
[17]   ORGANOLANTHANIDE HYDRIDE CHEMISTRY .3. REACTIVITY OF LOW-VALENT SAMARIUM WITH UNSATURATED-HYDROCARBONS LEADING TO A STRUCTURALLY CHARACTERIZED SAMARIUM HYDRIDE COMPLEX [J].
EVANS, WJ ;
BLOOM, I ;
HUNTER, WE ;
ATWOOD, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (05) :1401-1403
[18]   PARAMAGNETISM IN ORGANOLANTHANIDE COMPLEXES [J].
EVANS, WJ ;
HOZBOR, MA .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1987, 326 (03) :299-306
[19]   ORGANOLANTHANIDE HYDRIDE CHEMISTRY .1. SYNTHESIS AND X-RAY CRYSTALLOGRAPHIC CHARACTERIZATION OF DIMERIC ORGANOLANTHANIDE AND ORGANOYTTRIUM HYDRIDE COMPLEXES [J].
EVANS, WJ ;
MEADOWS, JH ;
WAYDA, AL ;
HUNTER, WE ;
ATWOOD, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (07) :2008-2014
[20]   THE ORGANOMETALLIC CHEMISTRY OF THE LANTHANIDE ELEMENTS IN LOW OXIDATION-STATES [J].
EVANS, WJ .
POLYHEDRON, 1987, 6 (05) :803-835