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Synthesis and Characterization of Sterically Expanded Ansa-η1-fluorenyl-amido Complexes by Levi J. Irwin; Joseph H. Reibenspies; Stephen A. Miller is a Chemistry article available to read on EtoBox.

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The octamethyloctahydrodibenzofluorenyl (Oct) ligand has been incorporated into twelve ansa-Oct-amido complexes having the general structures Me 2 Si(g 1 -C 29 H 36 )(g 1 -N-t Bu)MX 2 AE L or Me 2 Si(g 5 -C 29 H 36 )(g 1 -N-t Bu)MX 2 (M = Zr or Hf): 2 (X = Cl, L = Et 2 O); 3 (X = Br, L = Et 2 O); 4 (X = Me, L = Et 2 O); 5 (X = Me, L = THF); 6 (X = CH 2 Ph); and 7 (X = CH 2 SiMe 3 ). The solid-state structures have been determined for seven of these complexes by X-ray crystallography, revealing g 5 -C 29 H 36 coordination for the ether-free, pseudotetrahedral species 6-Zr, 6-Hf, and 7-Zr, but g 1 -C 29 H 36 coordination for the ether-bound, trigonal bipyramidal species 2-Zr, 3-Zr, 3-Hf, and 5-Zr. The unusual g 1 -C 29 H 36 coordination was assigned because only one metal-carbon bond in each structure was in the range of 2.281-2.330 A ̊; a second metal-carbon distance was found between 2.731 and 2.847 A ̊; the remaining metal-carbon distances were found between 3.130 and 4.029 A ̊. An increase in the hapticity of these and other Oct-and fluorenyl-containing compounds was correlated to a convergence in the carbon-carbon bond lengths within the relevant five-membered rings.

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Author

Levi J. Irwin; Joseph H. Reibenspies; Stephen A. Miller

Publisher

Elsevier Science; Elsevier ; Elsevier Ltd.; Elsevier BV (ISSN 0277-5387)

Published

2005

Language

EN

Field

Chemistry (Physical Sciences)