Co-ordination chemistry of bis(ferrocenylcarbaldimine) Schiff bases

Li, P., Scowen, I. J., Davies, J. E. and Halcrow, M. A. (1998) Co-ordination chemistry of bis(ferrocenylcarbaldimine) Schiff bases. Journal of the Chemical Society - Dalton Transactions, 17 (22). pp. 3791-3799. ISSN 0300-9246, 1477-9226

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The complex chemistries of 1,2-bis(ferrocen-1-ylmethyleneamino)ethane (L1), 1,2-bis(ferrocen-1-ylmethylene-amino)benzene (L2) and its 4-methyl (L3), 4-chloro (L4) and 4-nitro (L5) derivatives have been reexamined. Complexation of L1 by ZnCl2 afforded ZnCl2(L1), whose single crystal structure reveals a distorted tetrahedral zinc(II) centre with Zn � Fe 4.730(2) and 4.803(2) à . The complexes ZnCl2(L) (L = L2-L5), ZnBr2(L) (L = L2-L5) and CoBr2(L3) are accessible by MX2-templated condensation of 2 equivalents of ferrocenecarbaldehyde (fcCHO) with the appropriate 1,2-diaminobenzene. Treatment of Cu(NCMe)4X (X- = BF4- or PF6-) with L1, or fcCHO and the corresponding 1,2-diaminobenzene, yielded Cu(L)2X (L = L1-L3). The single crystal structure of Cu(L3)2-PF6·1.7CH2Cl 2 shows a tetrahedral copper(I) centre, the chelate ligands being substantially distorted from planarity. Compounds ZnCl2(L), ZnBr2(L) (L = L2-L5) and CoBr2(L3) exhibit weak electronic communication between the two ferrocenyl centres, showing by cyclic voltammetry two chemically reversible FeII-FeIII oxidations separated by 50-60 mV in CH2Cl2-0.5 M NBun4PF6 at 293 K; ZnCl2(L1) and Cu(L)2X (L = L1-L3) exhibit a single FeII-FeIII couple under these conditions. Attempted template syntheses of L2-L5 employing other MX2 (M = Mn, Co, Ni or Cu; X- = Cl-, Br-, NO3-, BF4- or ClO4-) salts yielded primarily 2-ferrocenylbenzimidazole intramolecular cyclisation derivatives; the crystal structure of one such product was determined.

Subjects:F Physical Sciences > F100 Chemistry
Divisions:College of Science > School of Chemistry
ID Code:13072
Deposited On:19 Mar 2014 17:52

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