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

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

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

@article{Wieser2002Effec-23730, title={Effects of an interannular bridge on spectral and electronic properties of bis(cyclopentadienyl)- and bis(indenyl)zirconium(IV) complexes}, year={2002}, doi={10.1021/om010770z}, 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} }

Leskelä, Markku Mäkelä, Nora I. Schaper, Frank Wieser, Ulrich Knuuttila, Hilkka R. Schaper, Frank Interconnection of the indenyl ligands of bis(indenyl)zirconium dichloride complexes by a 1,1'-positioned Me<sub>2</sub>Si or (CH<sub>2</sub>)<sub>2</sub> 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<sub>2</sub>Si bridge in otherwise analogous bis(cyclopentadienyl) complexes. Extended Hückel MO calculations show that overlap between the empty 4d orbitals of the ZrCl<sub>2</sub><sup>2+</sup> fragment and the highest filled π orbitals of the indenyl anions is decreased when a Me<sub>2</sub>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. 2002 Wieser, Ulrich Organometallics ; 21 (2002), 3. - S. 541-545 Mäkelä, Nora I. Brintzinger, Hans-Herbert Effects of an interannular bridge on spectral and electronic properties of bis(cyclopentadienyl)- and bis(indenyl)zirconium(IV) complexes Leskelä, Markku eng deposit-license 2013-06-24T17:08:56Z Brintzinger, Hans-Herbert 2013-06-24T17:08:56Z Knuuttila, Hilkka R.

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