| Autor: |
Brunker TJ; Inorganic Chemistry Laboratory, South Parks Road, Oxford, U.K., OX1 3QR., Hascall T, Cowley AR, Rees LH, O'Hare D |
| Jazyk: |
angličtina |
| Zdroj: |
Inorganic chemistry [Inorg Chem] 2001 Jun 18; Vol. 40 (13), pp. 3170-6. |
| DOI: |
10.1021/ic010125k |
| Abstrakt: |
The syntheses of the 4-coordinate Tp'MCl complexes (where M = Fe (1), Mn (2); and Tp' = hydrotris(3-isopropyl-4-bromopyrazolyl)borate) are described. The single-crystal X-ray structures show that the metal centers have distorted tetrahedral coordination. Analogous reaction of CrCl(2)(MeCN)(2) with TlTp' gave Cr(kappa(3)-Tp')(kappa(2)-Tp') (3) as the initial product. The 5-coordinate structure was assigned by single-crystal X-ray crystallography, and it was found that the kappa(3) ligand had isomerized to hydro(3-isopropyl-4-bromopyrazolyl)(2)(5-isopropyl-4-bromopyrazolyl)borate). 3 is labile in solution: in pentane it slowly converts to the 6-coordinate isomer Cr(kappa(3)-Tp')(2) (4), whose structure was determined by X-ray crystallography. In 4 both ligands are isomerized. Both 3 and 4 display Jahn-Teller distorted structures expected for high-spin d(4) configurations. Variable temperature magnetic susceptibility measurements confirm that 1, 2, and 3 all have high-spin electronic configurations in the range 5-300 K. In benzene solution 3 decomposes; one product [Cr(kappa(3)-Tp')(2)](+)[Tp'](-) (5), was identified by X-ray crystallography. 5 contains a pseudooctahedral Cr(III) cation with both ligands in the isomerized form and an uncoordinated Tp' ligand as counterion. Mechanistic studies reveal that this reaction is light rather than heat induced. IR spectroscopy is utilized to confirm the ligand hapticity in all complexes from the value of nu(B)(-)(H), and comparison is made with similar compounds. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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