Selective dimerization of terminal alkynes promoted by the cationic actinide compound [(Et2N)3U][BPh4].: Formation of the alkyne π-complex [(Et2N)2U(CCtBu) (η2-HCCtBu)][BP4]

被引:54
作者
Wang, JQ
Dash, AK
Berthet, JC
Ephritikhine, M
Eisen, MS [1 ]
机构
[1] Technion Israel Inst Technol, Dept Chem, IL-32000 Haifa, Israel
[2] CEA Saclay, CNRS URA 331, Serv Chim Mol, DRECAM,DSM, F-91191 Gif Sur Yvette, France
关键词
D O I
10.1021/om980973w
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The cationic actinide complex [(Et2N)(3)U]-[BPh4] is an active catalytic precursor for the selective dimerization of terminal alkynes. The regioselectivity is mainly toward the geminal dimer, but for bulky alkyne substituents the unexpected cis dimer is also obtained. Mechanistic NMR studies show that a eta(2)-pi-complex is formed between a terminal alkyne and an uranium-acetylide intermediate. This latter complex has been characterized spectroscopically. A plausible mechanistic scenario is proposed for the dimerization process.
引用
收藏
页码:2407 / 2409
页数:3
相关论文
共 21 条
[1]   SYNTHESIS OF CATIONIC URANIUM-COMPOUNDS BY PROTONOLYSIS OF AMIDE PRECURSORS - AMIDE AND CHLOROAMIDE COMPLEXES [J].
BERTHET, JC ;
BOISSON, C ;
LANCE, M ;
VIGNER, J ;
NIERLICH, M ;
EPHRITIKHINE, M .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1995, (18) :3019-3025
[2]   ''Link-functionalized'' polymers: An unusual macromolecular architecture through bifunctional initiation [J].
Boffa, LS ;
Novak, BM .
MACROMOLECULES, 1997, 30 (12) :3494-3506
[3]   REACTIONS OF YTTRIUM CARBON BONDS WITH ACTIVE HYDROGEN-CONTAINING MOLECULES - A USEFUL SYNTHETIC METHOD FOR PERMETHYLYTTROCENE DERIVATIVES [J].
DENHAAN, KH ;
WIELSTRA, Y ;
TEUBEN, JH .
ORGANOMETALLICS, 1987, 6 (10) :2053-2060
[4]   FIELD DESORPTION MASS-SPECTROMETRY STUDIES OF THE SAMARIUM-CATALYZED POLYMERIZATION OF ETHYLENE UNDER HYDROGEN [J].
EVANS, WJ ;
DECOSTER, DM ;
GREAVES, J .
MACROMOLECULES, 1995, 28 (23) :7929-7936
[5]   SYNTHESIS, REACTIVITY, AND STEREOCHEMISTRY OF N4-DIENE-MOLYBDENUM COMPLEXES - METALLOCYCLOPENTENE INTERMEDIACY IN AN INTRAMOLECULAR TRANS-CIS OLEFIN ISOMERIZATION [J].
FALLER, JW ;
ROSAN, AM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (14) :4858-4859
[6]  
FU PF, 1995, ORGANOMETALLICS, V117, P10747
[7]   The chemistry of enediynes, enyne allenes and related compounds [J].
Grissom, JW ;
Gunawardena, GU ;
Klingberg, D ;
Huang, DH .
TETRAHEDRON, 1996, 52 (19) :6453-6518
[8]   Controlling the catalytic oligomerization of terminal alkynes promoted by organoactinides: A strategy to short oligomers [J].
Haskel, A ;
Wang, JQ ;
Straub, T ;
Neyroud, TG ;
Eisen, MS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (13) :3025-3034
[9]   Oligomerization and cross-oligomerization of terminal alkynes catalyzed by organoactinide complexes [J].
Haskel, A ;
Straub, T ;
Dash, AK ;
Eisen, MS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (13) :3014-3024
[10]   REVERSIBLE CARBON-CARBON BOND FORMATION IN ORGANOLANTHANIDE SYSTEMS - PREPARATION AND PROPERTIES OF LANTHANIDE ACETYLIDES [CP-ASTERISK-2LNCCR]N AND THEIR REARRANGEMENT PRODUCTS [CP-ASTERISK-2LN]2(MU-ETA(2)-ETA(2)-RC4R) (LN = LA, CE, R = ALKYL) [J].
HEERES, HJ ;
NIJHOFF, J ;
TEUBEN, JH ;
ROGERS, RD .
ORGANOMETALLICS, 1993, 12 (07) :2609-2617