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• W2079156459 abstract "Bis(cyclopentadienyl) complexes (Cp2M) of the divalent first-row transition metals V−Ni have been known and used for over 50 years. For almost as long, an analogous series of compounds has been known with the indenyl ligand (i.e., Ind2M), with the conspicuous exception of M = Mn. Bis(indenyl) complexes of manganese(II), Ind′2MnLn, have now been synthesized by halide metathesis from MnCl2 and an appropriate potassium indenide. Depending on the indenyl ligand substituents and the presence of coordinated bases, a variety of structural motifs and bonding modes of the indenyl ligand are found in the resulting complexes. Single-crystal X-ray structures obtained for [2-(SiMe3)C9H6]2Mn, [1,3-(SiMe3)2C9H5]2Mn, and [1,3-(i-Pr)2C9H5]2Mn confirm that they possess classic η5-bound sandwich structures. In contrast, the unsubstituted parent complex recrystallizes from THF as a disolvate with two differently bonded indenyl ligands: i.e., (η3-C9H7)(η1-C9H7)Mn(thf)2. Without the coordinated solvent, density functional theory calculations suggest that the complex would have two slipped η5-bound ligands. When methyl groups are present on the benzo portion of the indenyl ligand, specifically in the 4,7-positions, the corresponding manganese complex is isolated as a cyclic octomer, {(4,7-Me2C9H5)2Mn}8, containing both bridging and terminal indenyl ligands. In the presence of 1,4-dioxane, however, attempted synthesis of (4,7-Me2C9H5)2Mn results in the isolation of the [K(dioxane)1.5][Mn(4,7-Me2C9H5)3] salt, in which each manganese atom is surrounded by a paddlewheel of three η2-bound 4,7-dimethylindenyl ligands. Cation−π bonding to the potassium and the presence of coordinated dioxane molecules generates a layered structure for the salt. Magnetic susceptibility measurements on the compounds indicate the presence of high-spin Mn(II) centers in all cases. These compounds demonstrate the high degree of conformational flexibility in the Mn(II)−indenyl bond." @default.
• W2079156459 created "2016-06-24" @default.
• W2079156459 creator A5027230273 @default.
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• W2079156459 date "2010-04-23" @default.
• W2079156459 modified "2023-10-03" @default.
• W2079156459 title "Indenyl Complexes of Manganese(II). Conformational Flexibility of the Manganese(II)−(R_<i>n</i>C₉H_7−<i>n</i>) Bond" @default.
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• W2079156459 doi "https://doi.org/10.1021/om100162j" @default.
• W2079156459 hasPublicationYear "2010" @default.
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