Abstract
The reactions of lithioferrocene (FcLi) and 1,1′-dilithioferrocene (fcLi 2) with the halfsandwich ruthenium complexes CpRu(CO) 2Cl, Cp★RU(CO) 2Cl and (C 6Me 6)Ru(CO)Cl 2 have been used to prepare the ferrocenyl compounds CpRu(CO) 2Fc ( 1), Cp★Ru(CO) 2Fc ( 2) and (C 6Me 6)Ru(CO)(Cl)Fc ( 3), as well as the ferrocenylene compounds [CpRu(CO) 2] 2fc ( 4) and [Cp★Ru(CO) 2] 2fc ( 5), respectively. Photodecarbonylation of 1 and 2 in the presence of two-electron ligands (L CN tBu ( a), PPh 3 ( b), PMe 3 (c)) leads to chiral complexes of the type Cp(★)Ru(CO)(L)Fc ( 1a– c, 2a– c); in the case of L CN tBu, further CO-substitution takes place to give Cp(★)Ru(CN t Bu) 2 Fc ( 1d, 2d). Photo-induced reaction of 3 with excess trimethylphosphane, PMe 3 ( c), produces the octahedral complex mer-[(PMe 3) 3Ru(CO)(Cl)Fc] ( 6), whereas organolithiums ( nBuLi and p-TolLi, but not FcLi) react with 3 to give (C 6Me 6)Ru(CO)(R)Fc (R = nBu ( 7a), p-Tol ( 7b)). Oxidation of 1, 2 and 3 by AgBF 4 leads to paramagnetic salts such as [Cp(★)Ru(CO) 2Fc]BF 4 ( 1e, 2e) and [(C 6Me 6)Ru(CO)(Cl)Fc]BF 4 ( 3e). All new complexes were characterized by IR, 1H and 13C NMR, and mass spectroscopy; the Cp and CP★ compounds were also studied by cyclovoltammetry.
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