Weakly bonded Lewis base adducts of plumbocene and stannocene: A synthetic and calculational study
- Univ. of Strathclyde, Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry
- Univ. of Cambridge (United Kingdom). Dept. of Chemistry; and others
The coordination of [({eta}-Cp){sub 2}Pb] and [({eta}-Cp){sub 2}Sn] by bidentate Lewis-base ligands gives the first examples of adducts of neutral p-block metallocenes. Ab initio MO calculations of [({eta}-Cp){sub 2}Pb{center_dot}TMEDA] (1) (TMEDA = (Me{sub 2}NCH{sub 2}){sub 2}), [Cp{sub 2}Pb{center_dot}4,4{prime}-Me{sub 2}bipy] (2) (4,4{prime}-Me{sub 2}bipy = 4,4{prime}-dimethylbipyridine) and the new complex [({eta}-Cp){sub 2}Sn{center_dot}TMEDA] (3) confirm that despite the presence of longer Pb-N and Sn-N bonds in the solid-state structures of the TMEDA adducts, the association of TMEDA with the metallocenes is more favorable than with 4,4{prime}-Me{sub 2}bipy. This finding is a consequence of the greater reorganization energy of 4,4{prime}-Me{sub 2}bipy compared to TMEDA. The low association energies of these species can be rationalized in terms of metal lone pair/ligand lone pair repulsion.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-97ER14758
- OSTI ID:
- 655370
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 15 Vol. 17; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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