UV photolysis of protonated ruthenium and osmium decamethylmetallocenes as a new method for synthesis of the metallonium cations

Abstract

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.

Synthesis, structures and reactions of some metallocene alcohols

“…Full-matrix least square refinements were carried out against F (on all data for 8 and 9; on data with I > 2rðIÞ for (10)(11)(12) using CRYS-R YS -TALS TALS [47]. Chebychev polynomial weighting schemes (five-term for 8; three-term for (9)(10)(11)(12) were applied [48]. Details of the data acquisition and refinements are summarised in Table 1; complete crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC 210126-210130 for compound 8-12. In the structure of 9 the half-molecule containing the atom Fe(2) was modelled with a disordered tert-butyl group [C(32), C(34) and C(36) with 33% occupancy; C(33), C(35) and C(37) 67% occupancy].…”

“…Many have been synthesised as precursors to metallocenestablised carbocations, which can be described as (g 5 -cyclopentadienyl-g 6 -fulvene)metal(II) and whose structures and bonding have been extensively studied [1][2][3][4][5][6][7][8][9][10][11][12], and which have themselves served as synthetic intermediates [12][13][14][15][16][17]. Metallocenyl alcohols have also been used as intermediates in the synthesis of chiral ligands for asymmetric catalysis [18,19].…”

New one-step methods for the synthesis of the metallonium dication [Ru(η5-C5Me5)(η5:σ:σ-C5Me3(CH2)2]2+ and its heteroannular analog starting from decamethylruthenoceneand its heteroannular analog starting from decamethylruthenocene

“…We also used broad-band UV photolysis for generating metallonium dications according to a procedure developed previously, 4 Our experiments demonstrated (control by the I H NMR spectra) that the reaction of ruthenocene 1 with pleura (method 1) as well as UV photolysis of ruthenocene 1 in CF3SO3H with the addition of a small amount of pleura (method 2) afforded two dications (Table 1). One of them was identified as the homoannular 1,2-dication [Ru(qS-CsMes)(qS:c:cyCsMea(CH2)2)] -~+ (4) (the structure of type B, M = Ru) based on the tact that the ~H and ~3C NMR spectra coincide with the published data on this cation.…”

Synthesis and properties of pentamethylmetallocene derivatives Cp*MCp (M = Ru, Fe). Crystal structure of the salt [CpRuC5Me4CH2 +OC6H2(NO2)3 -]

“…Re duction of the latter with LiAl(OBu t ) 3 leads to alcohol CpRuC 5 Me 4 CH 2 OH (4), which by the reaction with acids (CF 3 Table 1). An increase of the reaction time (up to 3 days) or temperature (50 °C, 3 h) leads to further oxidation of the methyl groups and transformation of cation 6 into the salt of triply charged cation [η 7 (CH 2 ) 2 C 5 Me 3 Ru(μ:η 5 ,η 5 C 5 H 4 C 5 H 4 )Ru(C 5 Me 4 CH 2 ) η 6 ] 3+ (7). A gradual increase in the content of cation 7 with simultaneous decrease in the relative amount of the initially formed cation 6 are observed in the solution (Scheme 1, see Table 1).…”