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UV photolysis of protonated ruthenium and osmium decamethylmetallocenes as a new method for synthesis of the metallonium cations I I [CsMesMC5MeICH2] + (M = Ru, Os) .4. A. Kamyshova,* A. Z. Kreindlin, M. L Rybinskaya, and P. V. PetrovskK A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813 Moscow, Russian Federation. Fax: + 7 (095) 135 5085 Decamethylmetallocenes Cp*2M (M = Ru, Os) in the presence of acids (CF3CO2H , CF3SO3H) give the protonation products ICP*2MHI+An -. Broad-band UV photolysis of 7-I their solutions results in the formation of the salts of oniu m carlons [Cp* MCsMe4C H2] *An-.A preparative procedure for the synthesis of these salts has been developed. Hydrolysis of the salts gives the carbinol Cp*MCsMe4CH2OH.

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Ferrocenium salts [(C5H5)2Fe]X (X = BF4, PF6) (I+·) react with tertiary phosphines PR3 (PMe3, PEt3, PnBu3, PMe2Ph, and PMePh2) in dichloromethane at room temperature to form a mixture of the corresponding ferrocenylphosphonium salts [(C5H5)FeC5H4PR3]X (III), ferrocene (I), and phosphonium salts [HPR3]X. The same reaction was carried out in an electrochemical cell as the electrolysis of a solution of ferrocene and phosphine in dichloromethane at the oxidation potential of ferrocene. Possible reaction pathways for phosphination of ferrocenium ion were studied by DFT at the M06‐L/6‐311++G(d,p) theory level. The experimental and theoretical studies of this reaction suggest it to proceed according to the Scheme of oxidative nucleophilic substitution of hydrogen in I+· including the following steps: a) nucleophilic exo addition of a phosphine to the cyclopentadienyl ring of I+· to form the radical cation adduct [(η5‐C5H5)Fe·(η4‐C5H5–+PR3)]X (II+·); b) redox reaction of the initial adduct II+· with the starting ferrocenium salt I+· to result in ferrocene (C5H5)2Fe (I) and iron phosphoniocyclopentadiene dication [(η5‐C5H5)Fe+(η4‐C5H5–+PR3)](X)2 (II2+) where the Csp3–H bond is involved in the agostic interaction with the metal atom; and c) deprotonation of the Csp3–H bond in II2+ by the starting phosphine to form III. The relation between the data obtained and current concepts of C–H functionalization in transition metal arene and cyclopentadienyl complexes is discussed.