COMMUNICATIONSCarbonyl addition reactions: To a solution of the cerium compound (1.5 mmol) in T H F ( 5 mL) cooled to -78'C, methyllithium (1.2 mmol, 0.75 mL of a 1 . 6~ solution in diethyl ether) was added. After 1 h the appropriate carbonyl derivative (2.0mmol) was added slowly and the mixture was stirred at -78°C for 30 min. Then, a saturated aqueous NH,CI solution (10 mL) was added, solid material war removed through a short pad of Celite, the Celite was rinsed with diethyl ether, and the ethereal solution was dried with MgSO,. The solvent was removed in vacuo and the residue purified by llash chromatography.

The magnetic anisotropy of the cyclic octanuclear Fe(III) cluster [Cs subsetFe(8)[N(CH(2)CH(2)O)(3)](8)]Cl was investigated. Based on a spin Hamiltonian formalism and the consequent use of all symmetries, the magnetic anisotropy could be calculated exactly to first order, i.e., in the strong exchange limit. Experimentally, the magnetic anisotropy was investigated by magnetic susceptibility and high-field torque magnetometry of single crystals. The field and angle dependence of the torque at 1.7 K could be accurately reproduced by the calculations with one single parameter set, providing accurate results for the coupling constant and single-ion zero-field-splitting. These magnetic parameters are compared to those of several related hexanuclear ferric wheels and are discussed with respect to magneto-structural correlations for both coupling constant and single-ion anisotropy.

The magnetic anisotropy of the two cyclic hexanuclear Fe(III) clusters [Li⊂Fe 6 L 6 ]Cl‚6CHCl 3 and [Na⊂Fe 6 L 6 ]-Cl‚6CHCl 3 , L ) N(CH 2 CH 2 O) 3 , was investigated. Based on a spin Hamiltonian formalism, the magnetic anisotropy was calculated exactly to first order, i.e., in the strong exchange limit, using Bloch's perturbational approach and irreducible tensor operator techniques. Experimentally, the magnetic anisotropy was investigated by magnetic susceptibility and high-field torque magnetometry of single crystals as well as inelastic neutron scattering. It is demonstrated that torque magnetometry provides a valuable tool for the study of magnetic anisotropy in spin cluster complexes. The experimental data could be accurately reproduced by the calculations, and the different methods yield consistent values for the coupling constants and zero-field-splitting parameters. Both the anisotropy and the exchange interaction parameter are found to increase with increasing Fe-O-Fe angle.

A simple template-mediated route, starting from triethalolamine 1, sodium hydride or caesium carbonate, and iron(III) chloride led to the six- and eight-membered iron coronates [Na c [Fe6[N(CH2CH2O)3]6]]+ (2) and [Cs c (Fe8[N(CH2CH2O)3]8]]+ (3). In the reaction of N-methyldiethanolamine 4 (H2L1) or N-(2,5-dimethylbenzyl)iminodiethanol 6 (H2L2) with calcium hydride followed by addition of a solution of iron(III) chloride, the neutral unoccupied coronands [Fe6Cl6(L1)6] (5) and [Fe6Cl6(L2)6] (7) were formed. Subsequent exchange of the chloride ions of 7 by bromide or thiocyanate ions afforded the ferric wheels [Fe6Br6(L2)6] (8) or [Fe6(NCS)6(L2)6] (9), respectively. Titration experiments of solutions of dianion (L1)2- with iron(III) chloride in THF revealed interesting mechanistic details about the self-assembling process leading to 5. At an iron/ligand ratio of 1:1.5 star-shaped tetranuclear [Fe[Fe(L1)2]3] (11) was isolated. However, at an iron/ligand ratio of 1:2, complex 11 was transformed into the ferric wheel 5. It was shown, that the interconversion of 5 and 11 is reversible. Based on the mechanistic studies, a procedure was developed which works for both the synthesis of homonuclear 11 and the star-shaped heteronuclear clusters [Cr[Fe(L1)2]3] (12) and [Al[Fe(L1)2]3] (13). The structures of all new compounds were determined unequivocally by single-crystal X-ray analyses.