A theoretical study on the complete catalytic cycle of the hetero-Pauson-Khand-type [2+2+1] cycloaddition reaction of ketimines, carbon monoxide and ethylene catalyzed by iron carbonyl complexes

被引:30
作者
Imhof, W
Anders, E
Göbel, A
Görls, H
机构
[1] Friedrich Schiller Univ Jena, Inst Anorgan & Analyt Chem, D-07743 Jena, Germany
[2] Friedrich Schiller Univ Jena, Inst Organ Chem & Makromol Chem, D-07743 Jena, Germany
关键词
cycloaddition; density functional calculations; homogeneous catalysis; iron; lactams;
D O I
10.1002/chem.200390134
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The [2+2+1] cycloaddition reaction of 1,4-diazabutadienes, carbon monoxide and ethylene catalyzed by iron carbonyl complexes produces pyrrolidin-2-one derivatives. Only one of the two imine moieties is activated during the catalysis. The mechanism of this cycloaddition reaction is studied by density functional theory at the B3LYP/6-311 + + G(d,p) level of theory. In accordance with experimental results, a [(diazabutadiene)Fe(CO)(3)] complex of square-pyramidal geometry is used as the starting compound S of the catalytic cycle. Based on experimental experience, the reaction with ethylene is considered to take place before any interaction with carbon monoxide. According to the computational results, the reaction does not proceed by ligand dissociation followed by addition of ethylene and subsequent intramolecular activation steps but by the approach of an ethylene molecule from the base of the square-pyramidal complex. This reaction yields an intermediate I-4 in which ethylene is coordinated to the iron centre and a new C-C bond between ethylene and one of the imine groups is formed. The insertion of a terminal carbon monoxide ligand into the metal-carbon bond between ethylene and iron produces the key intermediate I-7. The reaction proceeds by metal-assisted formation of a lactam P. The catalytic cycle is closed by a ligand-exchange reaction in which the diazabutadiene ligand substitutes P with reformation of S. This reaction pathway is found to be energetically favored over a reductive elimination. It leads to the experimentally observed heterocyclic product P and a reactive [Fe(CO)(3)] fragment.
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收藏
页码:1166 / 1181
页数:16
相关论文
共 139 条
[1]   Bonding properties of a novel inorganometallic complex, Ru(SnPh(3))(2)(CO)(2)(iPr-DAB) (iPr-DAB=N,N'-diisopropyl-1,4-diaza-1,3-butadiene), and its stable radical-anion, studied by UV-Vis, IR, and EPR spectroscopy, (spectro-) electrochemistry, and density functional calculations [J].
Aarnts, MP ;
Wilms, MP ;
Peelen, K ;
Fraanje, J ;
Goubitz, K ;
Hartl, F ;
Stufkens, DJ ;
Baerends, EJ ;
Vlcek, A .
INORGANIC CHEMISTRY, 1996, 35 (19) :5468-5477
[2]   Syntheses, structures and spectroscopic properties of a novel series of metal-metal bonded complexes Ru(E)(E')(CO)(2)(Pr-i-DAB):(E=Br, E'=Mn(CO)(5); E=SnPh3, E'=Mn(CO)(5), Re(CO)(5), Co(CO)(4); E=Me, E'=Re(CO)(5); E=E'=Mn(CO)(5), Re(CO)(5); Pr-i-DAB=N,N'-diisopropyl-1,4-diaza-1,3-butadiene) [J].
Aarnts, MP ;
Oskam, A ;
Stufkens, DJ ;
Fraanje, J ;
Goubitz, K ;
Veldman, N ;
Spek, AL .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 531 (1-2) :191-205
[3]  
Alper P. B., 1999, ANGEW CHEM, V111, P3379
[4]  
Alper PB, 1999, ANGEW CHEM INT EDIT, V38, P3186, DOI 10.1002/(SICI)1521-3773(19991102)38:21<3186::AID-ANIE3186>3.3.CO
[5]  
2-5
[6]   A MOLECULAR-ORBITAL STUDY OF METHYL MIGRATION IN PENTACARBONYLMETHYLMANGANESE(I) [J].
AXE, FU ;
MARYNICK, DS .
ORGANOMETALLICS, 1987, 6 (03) :572-580
[7]   CHEMICAL ORIGINS OF SUBSTITUENT EFFECTS IN ALKYLPENTACARBONYLMANGANESE(I) GROUP MIGRATION REACTIONS [J].
AXE, FU ;
MARYNICK, DS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (12) :3728-3734
[8]   Identification and treatment of internal rotation in normal mode vibrational analysis [J].
Ayala, PY ;
Schlegel, HB .
JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (06) :2314-2325
[9]   17-ELECTRON METAL-CENTERED RADICALS [J].
BAIRD, MC .
CHEMICAL REVIEWS, 1988, 88 (07) :1217-1227
[10]   ASSOCIATIVE SUBSTITUTION-REACTIONS OF METAL-CARBONYLS [J].
BASOLO, F .
INORGANICA CHIMICA ACTA-ARTICLES AND LETTERS, 1985, 100 (01) :33-39