Abstract
Complexes of the type (CO)2(PR3)2Fe-η2-CS2, known to yield different coupling products with alkynes, are studied. In particular two products, the metallocycle L4Fe-C(S)C(R)C(R)S and the 1,3-dithiol-2-ylidene L4Pe-CSC(R)C(R)S, isomerize easily and, for an appropriate choice of the phosphine ligands, are in equilibrium. Extended Hückel calculations and qualitative MO theory are used to analyze the electronic features of these compounds and their possible interconversion pathways. The study illustrates the major orbital effects and, indirectly, the electrostatic effects that may become selective at a certain point of the reaction.
| Original language | English |
|---|---|
| Pages (from-to) | 1921-1928 |
| Number of pages | 8 |
| Journal | Organometallics |
| Volume | 8 |
| Issue number | 8 |
| Publication status | Published - 1989 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Reactivity of alkynes toward M-η2-CS2 metal complexes. 2. A theoretical discussion on the coupling products obtainable with iron fragments and their relative stability. / Li, Jing; Hoffmann, Roald; Mealli, Carlo; Silvestre, Jérôme.
In: Organometallics, Vol. 8, No. 8, 1989, p. 1921-1928.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Reactivity of alkynes toward M-η2-CS2 metal complexes. 2. A theoretical discussion on the coupling products obtainable with iron fragments and their relative stability
AU - Li, Jing
AU - Hoffmann, Roald
AU - Mealli, Carlo
AU - Silvestre, Jérôme
PY - 1989
Y1 - 1989
N2 - Complexes of the type (CO)2(PR3)2Fe-η2-CS2, known to yield different coupling products with alkynes, are studied. In particular two products, the metallocycle L4Fe-C(S)C(R)C(R)S and the 1,3-dithiol-2-ylidene L4Pe-CSC(R)C(R)S, isomerize easily and, for an appropriate choice of the phosphine ligands, are in equilibrium. Extended Hückel calculations and qualitative MO theory are used to analyze the electronic features of these compounds and their possible interconversion pathways. The study illustrates the major orbital effects and, indirectly, the electrostatic effects that may become selective at a certain point of the reaction.
AB - Complexes of the type (CO)2(PR3)2Fe-η2-CS2, known to yield different coupling products with alkynes, are studied. In particular two products, the metallocycle L4Fe-C(S)C(R)C(R)S and the 1,3-dithiol-2-ylidene L4Pe-CSC(R)C(R)S, isomerize easily and, for an appropriate choice of the phosphine ligands, are in equilibrium. Extended Hückel calculations and qualitative MO theory are used to analyze the electronic features of these compounds and their possible interconversion pathways. The study illustrates the major orbital effects and, indirectly, the electrostatic effects that may become selective at a certain point of the reaction.
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UR - http://www.scopus.com/inward/citedby.url?scp=0011674554&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0011674554
VL - 8
SP - 1921
EP - 1928
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 8
ER -