RESUMEN
The trinuclear ferrocenophane [{Fe(eta(5)-C(5)H(4))(3)}(2)Ga(2)] (3) featuring two sp(2)-hybridized gallium atoms in bridging positions between three ferrocene-1,1'-diyl units represents a novel type of ferrocene derivative. Compound 3 is obtained by thermal treatment of 1,1'-bis(dimethylgallyl)ferrocene (1) in nondonor solvents or in diethyl ether as solvent and subsequent thermal decomplexation. The [1.1]ferrocenophane [{Fe(eta(5)-C(5)H(4))(2)}(2){GaMe}(2)] (2) is an intermediate in the formation of 3. The reaction of 3 with an excess of trimethylgallium leads back to 1 and proves the reversibility of the multistep reaction sequence. Theoretical calculations reveal a carousel-type D(3h) structure for 3. The compound can best be described as being composed of three only weakly interacting ferrocenediyl units covalently connected by gallium atoms without any pi-bond contribution in the Ga--C bonds. Owing to steric constraints 3 cannot be reduced to the dianion 3(2-), which would feature a Ga--Ga bond. Compound 3 represents a stereochemically rigid difunctional Lewis acid allowing the formation of the adducts 3 a-3 d possessing linear donor-aceptor-aceptor-donor arrangements. Crystal structure data for 3 a-3 d show a symmetry-reduced chiral ferrocenophane core (D(3h)-->D(3)). A polymeric rodlike structure is observed for 3 b and 3 d caused by pi-stacking effects (3 b) or by a difunctional donor-acceptor interaction (3 d). In solution, the chirality of the adducts is lost by rapid interconversion of the enantiomers. A cyclic voltammogram of 3 b in pyridine reveals three quasi-reversible oxidation steps at -356, -154, and 8 mV, indicating only weak electron delocalization in the cationic species. The redox potentials of the pyridine adduct 3 b are compared with those of other pyridine-stabilized gallyl-sustituted ferrocene derivatives and with ferrocene itself.
RESUMEN
The 1,4-diphosphabuta-1,3-diene (DPB) ligand as a tool for stabilizing anionic group 13 (B, Al, Ga) and neutral group 14 (C, Si, Ge) cyclic Arduengo-type carbenes is studied by quantum chemical calculations at density functional level. Accordingly, for the former group this ligand is better suited than the corresponding 1,4-diazabuta-1,3-diene (DAB) ligand. It results in larger electron affinities for the corresponding doublet states. For the latter group the DPB ligand yields essentially smaller singlet-triplet separations than the DAB ligand. An exception is the anionic boron compound with relative low singlet stability for both the DAB and DPB ligands.