Bonding and conformational aspects of thiolato-bridged early-late heterobimetallics

Roger Rousseau, Douglas W. Stephan

Research output: Contribution to journalArticle

36 Citations (Scopus)

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 languageEnglish
Pages (from-to)3399-3403
Number of pages5
JournalOrganometallics
Volume10
Issue number9
Publication statusPublished - 1991

Fingerprint

Metals
metals
Conformations
Electrons
axioms
Electrochemical properties
folding
Structural properties
indication
electrons
Atoms
Geometry
geometry
atoms
interactions

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 journalArticle

@article{163a1efcfcf743dbac1ac65e6f39135f,
title = "Bonding and conformational aspects of thiolato-bridged early-late heterobimetallics",
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.",
author = "Roger Rousseau and Stephan, {Douglas W.}",
year = "1991",
language = "English",
volume = "10",
pages = "3399--3403",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "9",

}

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.

UR - http://www.scopus.com/inward/record.url?scp=0000242581&partnerID=8YFLogxK

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 -