Search

The novel tetrahedral clusters (μ3-CR)Co2M(CO)8(η5-Ind) (M=Mo,W; R=H, CH3, C6H5, COOC2H5) 5–12 containing the indenyl ligand were isolated from reactions of tricobalt clusters (μ3-CR)Co3(CO)9 (R=H, CH3, C6H5, COOC2H5) and K(η5-Ind)M(CO)3 (M=Mo,W) under mild conditions. The cluster complex (μ3-CC6H5)CoMo2(CO)7(η5-Ind)(η5-Cp (Cp*=C5H4C(O)CH3) 16 was obtained via the stepwise metal exchange reaction of complex (μ3-CC6H5)Co2Mo(CO)8(η5-Ind) 9 with Na(η5-CpMo(CO)3, but the reaction of (μ3-CC6H5)Co2Mo(CO)8(η5-Cp*) 15 with K(η5-Ind)Mo(CO)3 yielded only 9. The crystal structures of compounds 7, 9 and 13 were established by single crystal X-ray diffraction methods and show structural evidence for “slippage” of the indenyl ring. [Copyright &y& Elsevier]

Six new cluster derivatives [Rh2Co2(CO)6(μ-CO)4(μ4,η2-HC&z.tbnd6;CR)] (R=FeCp2 1, CH2OH 2, (CH3O)C10H6CH(CH3)COOCH2C&z.tbnd6;CH 3) and [RhCo3(CO)6(μ-CO)4(μ4,η2-HC&z.tbnd6;CR)] (R=FeCp2 4, CH2OH 5, (CH3O)C10H6CH(CH3)COOCH2C&z.tbnd6;CH 6) were obtained by the reactions of [Rh2Co2(CO)12] and [RhCo3(CO)12] with substituted 1-alkyne ligands HC&z.tbnd6;CR [R=FeCp2 7, CH2OH 8, (CH3O)C10H6CH(CH3) COOCH2C&z.tbnd6;CH 9] in n-hexane at room temperature, respectively. Alkynes insert into the Co&z.sbnd;Co bond of the tetranuclear clusters to give butterfly clusters. [Rh2Co2(CO)6(μ-CO)4(μ4,η2-HC&z.tbnd6;CFeCp2)] (1) was characterized by a single-crystal X-ray diffraction analysis. Reactions of 1, 2 with 7, 8 and ambient pressure of carbon monoxide at 25 °C gave two known cluster complexes [Co2(CO)6(μ2, η2-HC&z.tbnd6;CR)] (R=FeCp2 10, CH2OH 11), respectively. All clusters were characterized by element analysis, IR and 1H-NMR spectroscopy. [Copyright &y& Elsevier]

Six new Rh&z.sbnd;Co mixed-metal linked cluster complexes [Rh2Co2(CO)8(μ-CO)2 (μ4,η2-HC&z.tbnd6;CCH2O&z.sbnd;)]2R (R=C6H4-1,4 (1); C6H4-1,4(C(O))2 (2); (C(O)CH2)2 (3); (C(O)CH)2 (4); (C(O))2CH2 (5); (C(O))2 (6)) have been synthesized from reactions of [Rh2Co2(CO)12] (7) with the appropriate diyne compounds [(HC&z.tbnd6;CCH2CO)&z.sbnd;]2R (R=C6H4-1,4 (8); C6H4-1,4(C(O))2 (9); (C(O)CH2)2 (10); (C(O)CH)2 (11); (C(O))2CH2 (12); (C(O))2 (13)) in n-hexane at room temperature, respectively. The acetylene moieties of diyne ligands insert into the Co&z.sbnd;Co bonds of two tetranuclear clusters to give linked octahedral clusters containing two [Rh2Co2C2] units. The structure of cluster 1 was determined by single-crystal X-ray diffraction analysis and all clusters were characterized by elemental analysis (C/H), IR and 1H-NMR spectroscopy. [Copyright &y& Elsevier]