New thiocyanato and azido adducts of the redox-active Fe(eta(5)-C5Me5)(eta(2)-dppe) center: Synthesis and study of the Fe(II) and Fe(III) complexes

作者：Malvolti Floriane; Trujillo Alexander; Cador Olivier; Gendron Frederic; Costuas Karine; Halet Jean Francois; Bondon Arnaud; Toupet Loic; Molard Yann; Cordier Stephane; Paul Frederic^*

来源：Inorganica Chimica Acta, 2011, 374(1): 288-301.

DOI：10.1016/j.ica.2011.03.002

• Organometallics
• Thiocyanato complex
• Azido complex
• Spin delocalization
• Magnetic anisotropy
• ESR

The new thiocyanato- (5) and azido- (6) complexes were synthesized and studied under their Fe(II) and Fe(III) redox states. For the first time among the various [Fe(eta(5)-C5Me5)(eta(2)-dppe)]-based cationic radicals studied so far, the magnitude and spatial orientation of the g-tensor diagonal values were experimentally determined for 5[PF6]. These data are in good agreement with those issued from a DFT modelization. The changes experienced by the electronic structure of the Fe(II) complexes subsequent to oxidation are reminiscent of these previously observed for the known arylalkynyl analogues, albeit some differences can be pointed out. Thus, the differences observed in the H-1 NMR spectra of 5[PF6] and 6[PF6] are attributed to a slower electronic spin relaxation and to the differently oriented magnetic anisotropy. The sizeable spin density evidenced by DFT on the terminal atom of the ligands of the Fe(III) complexes renders these new paramagnetic metallo-ligands quite appealing for accessing larger polynuclear molecular assemblies with magnetically interacting centers.

• 出版日期2011-8-1