Abstract
Extended Huckel and Fenske-Hall MO calculations have been used to examine the bonding in a series of thiolato-bridged early-late heterobimetallics. The calculations support the postulate of a weak, dative interaction between the electron-rich late metal and the electron-deficient early metal center. Generally, for Ti species the interaction is weak σ bonding in character, although for Zr there is an indication of an additional π component. When the coordination sphere of the late metal center is trigonal or square planar, these interactions result in a MS2M′ core folding and an endo-cisoid conformation of the substituents on the bridging S atoms is adopted. Alternatively, a endo-transoid conformation and a planar MS2M′ core is seen when the late metal center requires a pseudotetrahedral coordination geometry. The implications of these results with respect to the structural and electrochemical properties is considered.
| Original language | English |
|---|---|
| Pages (from-to) | 3399-3403 |
| Number of pages | 5 |
| Journal | Organometallics |
| Volume | 10 |
| Issue number | 9 |
| Publication status | Published - 1991 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Organic Chemistry
Cite this
Bonding and conformational aspects of thiolato-bridged early-late heterobimetallics. / Rousseau, Roger; Stephan, Douglas W.
In: Organometallics, Vol. 10, No. 9, 1991, p. 3399-3403.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Bonding and conformational aspects of thiolato-bridged early-late heterobimetallics
AU - Rousseau, Roger
AU - Stephan, Douglas W.
PY - 1991
Y1 - 1991
N2 - Extended Huckel and Fenske-Hall MO calculations have been used to examine the bonding in a series of thiolato-bridged early-late heterobimetallics. The calculations support the postulate of a weak, dative interaction between the electron-rich late metal and the electron-deficient early metal center. Generally, for Ti species the interaction is weak σ bonding in character, although for Zr there is an indication of an additional π component. When the coordination sphere of the late metal center is trigonal or square planar, these interactions result in a MS2M′ core folding and an endo-cisoid conformation of the substituents on the bridging S atoms is adopted. Alternatively, a endo-transoid conformation and a planar MS2M′ core is seen when the late metal center requires a pseudotetrahedral coordination geometry. The implications of these results with respect to the structural and electrochemical properties is considered.
AB - Extended Huckel and Fenske-Hall MO calculations have been used to examine the bonding in a series of thiolato-bridged early-late heterobimetallics. The calculations support the postulate of a weak, dative interaction between the electron-rich late metal and the electron-deficient early metal center. Generally, for Ti species the interaction is weak σ bonding in character, although for Zr there is an indication of an additional π component. When the coordination sphere of the late metal center is trigonal or square planar, these interactions result in a MS2M′ core folding and an endo-cisoid conformation of the substituents on the bridging S atoms is adopted. Alternatively, a endo-transoid conformation and a planar MS2M′ core is seen when the late metal center requires a pseudotetrahedral coordination geometry. The implications of these results with respect to the structural and electrochemical properties is considered.
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UR - http://www.scopus.com/inward/citedby.url?scp=0000242581&partnerID=8YFLogxK
M3 - Article
VL - 10
SP - 3399
EP - 3403
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 9
ER -