Effects of an interannular bridge on spectral and electronic properties of bis(cyclopentadienyl)- and bis(indenyl)zirconium(IV) complexes

Wieser, Ulrich; Schaper, Frank; Brintzinger, Hans-Herbert; Mäkelä, Nora I.; Knuuttila, Hilkka R.; Leskelä, Markku

Effects of an interannular bridge on spectral and electronic properties of bis(cyclopentadienyl)- and bis(indenyl)zirconium(IV) complexes

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Datum

2002

Autor:innen

Wieser, Ulrich

Schaper, Frank

Brintzinger, Hans-Herbert

Mäkelä, Nora I.

Knuuttila, Hilkka R.

Leskelä, Markku

Publikationstyp

Zeitschriftenartikel

unikn.publication.listelement.citation.prefix.version.undefined

Organometallics. 2002, 21(3), pp. 541-545. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om010770z

Zusammenfassung

Interconnection of the indenyl ligands of bis(indenyl)zirconium dichloride complexes by a 1,1'-positioned Me₂Si or (CH₂)₂ bridge causes pronounced bathochromic shifts of the longest wavelength UV/vis absorption bands by ca. 50 nm, while much smaller shifts are caused by a Me₂Si bridge in otherwise analogous bis(cyclopentadienyl) complexes. Extended Hückel MO calculations show that overlap between the empty 4d orbitals of the ZrCl₂²⁺ fragment and the highest filled π orbitals of the indenyl anions is decreased when a Me₂Si bridge forces the indenyl ligands into a lateral orientation. Consequences of this orbital mismatch, e.g. on electron densities at the Zr center, are discussed.

Fachgebiet (DDC)

540 Chemie

Zitieren

ISO 690

WIESER, Ulrich, Frank SCHAPER, Hans-Herbert BRINTZINGER, Nora I. MÄKELÄ, Hilkka R. KNUUTTILA, Markku LESKELÄ, 2002. Effects of an interannular bridge on spectral and electronic properties of bis(cyclopentadienyl)- and bis(indenyl)zirconium(IV) complexes. In: Organometallics. 2002, 21(3), pp. 541-545. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om010770z

BibTex

@article{Wieser2002Effec-23730,
  year={2002},
  doi={10.1021/om010770z},
  title={Effects of an interannular bridge on spectral and electronic properties of bis(cyclopentadienyl)- and bis(indenyl)zirconium(IV) complexes},
  number={3},
  volume={21},
  issn={0276-7333},
  journal={Organometallics},
  pages={541--545},
  author={Wieser, Ulrich and Schaper, Frank and Brintzinger, Hans-Herbert and Mäkelä, Nora I. and Knuuttila, Hilkka R. and Leskelä, Markku}
}

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    <dcterms:abstract xml:lang="eng">Interconnection of the indenyl ligands of bis(indenyl)zirconium dichloride complexes by a 1,1'-positioned Me&lt;sub&gt;2&lt;/sub&gt;Si or (CH&lt;sub&gt;2&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt; bridge causes pronounced bathochromic shifts of the longest wavelength UV/vis absorption bands by ca. 50 nm, while much smaller shifts are caused by a Me&lt;sub&gt;2&lt;/sub&gt;Si bridge in otherwise analogous bis(cyclopentadienyl) complexes. Extended Hückel MO calculations show that overlap between the empty 4d orbitals of the ZrCl&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;2+&lt;/sup&gt; fragment and the highest filled π orbitals of the indenyl anions is decreased when a Me&lt;sub&gt;2&lt;/sub&gt;Si bridge forces the indenyl ligands into a lateral orientation. Consequences of this orbital mismatch, e.g. on electron densities at the Zr center, are discussed.</dcterms:abstract>
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