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 ZrCl2
2+ 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.
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